Macrocyclic Polyradicaloids with Unusual Super-ring ......Gopalakrishna, Hoa Phan, Naoki Aratani,...

Chem, Volume 4

Supplemental Information

Macrocyclic Polyradicaloids with Unusual

Super-ring Structure and Global Aromaticity

Chunchen Liu, María Eugenia Sandoval-Salinas, Yongseok Hong, Tullimilli Y.Gopalakrishna, Hoa Phan, Naoki Aratani, Tun Seng Herng, Jun Ding, HirokoYamada, Dongho Kim, David Casanova, and Jishan Wu

S1

Supplementary Information for

Macrocyclic Polyradicaloids with Unusual Super-ring

Structure and Global Aromaticity

Chunchen Liu, María Eugenia Sandoval-Salinas, Yongseok Hong, Tullimilli Y.

Gopalakrishna, Hoa Phan, Naoki Aratani, Tun Seng Herng, Jun Ding, Hiroko Yamada,

Dongho Kim,* David Casanova* and Jishan Wu*

Correspondence to: [email protected] (J.W.); [email protected] (D.C.);

[email protected] (D.K.)

Table of Contents

1. Materials and methods∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S2

1.1. General experimental methods∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S2

1.2 Synthetic procedure and characterization data∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S3

1.3 Additional spectra and figures∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S5

2. Theoretical calculations∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S23

3. X-ray crystallographic data ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S39

4. Additional NMR and mass spectra of intermediate compounds∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S43

5. References∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S49

6. Appendix: Cartesian coordinates of the optimized geometry………………………..S51

mailto:[email protected]



S2

1. Materials and methods

1.1. General experimental methods

All reagents and catalysts were obtained from the commercial suppliers and used

without further purification. Anhydrous dichloromethane (DCM) and toluene were

obtained from solvent purification systems from LC Technology Solutions Inc. Anhydrous

tetrahydrofuran (THF) was freshly distilled over sodium/benzophenone prior to use. 2-

Mesitylmagnesium bromide (1M in THF) was purchased from Sigma-Aldrich. The 1H

NMR and 13C NMR spectra were obtained on Bruker DPX 300/500 NMR spectrometer

with tetramethylsilane (TMS) as internal standard. MALDI-TOF mass spectra (MS) were

obtained on a Bruker Autoflex instrument with dithranol or tetracyanoquinodimethane

(TCNQ) as matrix. High-resolution (HR) APCI and ESI mass spectra were recorded on a

Bruker amazon X mass spectrometer. UV-vis-NIR absorption spectra were obtained on a

Shimadzu UV-3600 plus spectrometer. The electrochemical measurements (cyclic

voltammetry (CV) and differential pulse voltammetry (DPV)) were conducted in

anhydrous DCM with 0.1 M tetra-n-butyammoniumhexafluorophosphate (n-Bu4NPF6) as

supporting electrolyte at room temperature under inert atmosphere. A gold stick, a platinum

wire and Ag/AgCl (3M KCl solution) were used as working electrode, counter electrode

and reference electrode, respectively. The potential was externally calibrated against the

ferrocene/ferrocenium (Fc/Fc+) couple. Continuous wave X-band ESR spectra were

measured on a JEOL (FA200) spectrometer.

A Quantum Design 7 Telsa superconducting quantum interference device

magnetometer (SQUID-VSM) was used for the magnetic measurements. Solid sample of

compound with a weight of 8-10 mg was sealed in a plastic capsule. Considering the

stability of the compound, the magnetic susceptibility was measured in the temperature

range from 2 K to 300 K with an applied field of 0.5 T. After correction of diamagnetic

contributions from the sample, using tabulated constants, sample holder and paramagnetic

contamination the magnetic data were fitted with the following equation:

𝜒𝑇 = 𝑁𝑔2𝛽2

𝑘∗

𝐴

𝐵

For such a complicated polyradicaloid system, we cannot simply apply Bleaney-Bowers

equation to fit the data. Alternatively, the data was fitted by considering the relative energy

between each spin states (calculated by RAS-SF method, Figure S19).

For 8MC-M:

A = 2exp((-26.93x)/(kT)) + 2exp((-32.33x)/(kT)) + 2exp((-32.37x)/(kT)) + 2exp((-

49.08x)/(kT)) + 2exp((-49.14x)/(kT)) + 2exp((-56.65x)/(kT)) + 2exp((-32.37x)/(kT)) +

2exp((-57.23x)/(kT)) + 8exp((-52.49x)/(kT)) + 8exp((-69.84x)/(kT)) + 8exp((-71.64x)/(kT))

+ 8exp((-72.76x)/(kT)) + 8exp((-75.57x)/(kT))

B =1 + exp((-34.64x)/(kT)) + exp((-43.37x)/(kT)) + exp((-48.58x)/(kT)) + 2exp((-


3exp((-49.08x)/(kT)) + 3exp((-49.14x)/(kT)) + 3exp((-56.65x)/(kT)) + 3exp((-


5exp((-71.64x)/(kT)) + 5exp((-72.76x)/(kT)) + 5exp((-75.57x)/(kT))

For 10MC-M:

S3

A = 2 + 2exp((-9.67x)/(kT)) + 2exp((-10.35x)/(kT)) + 2exp((-20.87x)/(kT)) + 2exp((-


20exp((-67.37x)/(kT)) + 20exp((-89.43x)/(kT))

B = 3 + exp((-4.14x)/(kT)) + exp((-10.88x)/(kT)) + exp((-26.74x)/(kT)) + exp((-

28.65x)/(kT)) + exp((-37.50x)/(kT)) + 3exp((-9.67x)/(kT)) + 3exp((-10.35x)/(kT)) +

3exp((-20.87x)/(kT)) + 3exp((-25.59x)/(kT)) + 5exp((-15.24x)/(kT)) + 5exp((-

27.78x)/(kT)) + 5exp((-29.73x)/(kT)) + 5exp((-39.34x)/(kT)) + 7exp((-67.36x)/(kT))

The femtosecond time-resolved transient absorption (fs-TA) spectrometer consists of an

optical parametric amplifier (OPA; Palitra, Quantronix) pumped by a Ti: sapphire

regenerative amplifier system (Integra-C, Quantronix) operating at 1 kHz repetition rate

and an optical detection system. The generated OPA pulses have a pulse width of ~100 fs

and an average power of 1 mW in the range of 280-2700 nm, which are used as pump

pulses. White light continuum (WLC) probe pulses were generated using a sapphire

window (3 mm thick) by focusing a small portion of the fundamental 800 nm pulses, which

was picked off by a quartz plate before entering the OPA. The time delay between pump

and probe beams was carefully controlled by making the pump beam travel along a variable

optical delay (ILS250, Newport). Intensities of the spectrally dispersed WLC probe pulses

are monitored by a High Speed Spectrometer (Ultrafast Systems) for both visible and near-

infrared measurements. To obtain the time-resolved transient absorption difference signal

(ΔA) at a specific time, the pump pulses were chopped at 500 Hz and absorption spectra

intensities were saved alternately with or without pump pulse. Typically, 4000 pulses

excite the samples to obtain the fs-TA spectra at each delay time. The polarization angle

between pump and probe beam was set at the magic angle (54.7o) using a Glan-laser

polarizer with a half-wave retarder in order to prevent polarization-dependent signals.

Cross-correlation fwhm in pump-probe experiments was less than 200 fs and chirp of WLC

probe pulses was measured to be 800 fs in the 400-800 nm region. To minimize chirp, all

reflection optics in the probe beam path and a quartz cell of 2 mm path length were used.

After fs-TA experiments, the absorption spectra of all compounds were carefully examined

to detect if there were artifacts due to degradation and photo-oxidation of samples. The

three-dimensional data sets of ΔA versus time and wavelength were subjected to singular

value decomposition and global fitting to obtain the kinetic time constants and their

associated spectra using Surface Xplorer software (Ultrafast Systems).

1.2. Synthetic procedure and characterization data

Compounds 8MC-CHO and 10MC-CHO. A three-necked round bottom flask was

charged with 4,6-dibromobenzene-1,3-dicarbaldehyde 1 (300 mg, 1.03 mmol) and 1,3-

benzenediboronic acid 2 (170.4 mg, 1.03 mmol), NaHCO3(6.9 g, 82.4 mmol, in 15 mL

water), tetrahydrofuran (400 mL) and purged with argon for 30 mins. Pd2(dba)3(94.2 mg,

0.1 mmol) and tri-tert-butylphosphoniumtetrafluoroborate ([(t-Bu)3PH]BF4) (119.4 mg,

0.41 mmol) were added subsequently under argon. The resultant mixture was degassed by

three freeze-pump-thaw cycles and then heated at 85 oC for 3 days. After cooling to room

temperature, the THF was evaporated and water was added in the reaction mixture. After

extraction of the reaction mixture with chloroform followed by drying over sodium sulfate,

the solvent was evaporated to dryness. The desired 8MC-CHO and 10MC-CHO can be

S4

observed from the MALDI-TOF mass spectrum of the obtained crude products as shown

in Figure S2. The crude mixture was first passed through a silica gel column (chloroform)

followed by a Recycling Preparative Gel Permeation Chromatography purification (GPC,

from Japan Analytical Industry Co., Ltd.). Pure 8MC-CHO and 10MC-CHO were

successfully isolated in 24% and 10% yield, respectively. The structures of both were also

confirmed by X-ray crystallographic analysis of single crystals grown from THF/methanol

(see later part for details).

8MC-CHO: 1H NMR (CDCl3, 500 MHz): δ ppm 10.11 (s, 8H), 8.60 (s, 4H), 7.63 (t, J =

4.6 Hz, 8H), 7.59 (s, 4H), 7.55 (d, J = 1.8 Hz, 4H), 7.53 (s, 4H). 13C NMR (CDCl3, 125

MHz): δ ppm 190.22, 148.50, 137.91, 134.08, 133.55, 130.82, 129.54, 128.73, 29.86.

HRMS (APCI, m/z): [(M+H)+] calcd for C56H32O8, 833.2172; found, 833.2170.

10MC-CHO: 1H NMR (CDCl3, 400 MHz): δ ppm 10.04 (s, 10H), 8.55 (s, 5H), 7.63 (t, J

= 8.3 Hz, 5H), 7.52 (dd, 3J = 7.3 Hz, 4J = 1.7 Hz, 10H), 7.50 (s, 5H), 7.47 (d, J = 4.86 Hz,

5H). 13C NMR (CDCl3, 100 MHz): δ ppm 190.14, 148.15, 137.40, 133.41, 130.51, 130.06,

129.67, 128.96, 29.69. HRMS (APCI, m/z): [(M+H)+] calcd for C70H40O10, 1040.2625;

found, 1040.2627.

Compounds 8MC-H and 10MC-H. Compound 8MC-CHO (10 mg, 0.012 mmol) or

10MC-CHO (10 mg, 0.01 mmol) was dissolved in 10 mL of anhydrous THF under argon

atmosphere. 2-Mesitylmagnesium bromide (1M solution in THF, 80 equivalents for 8MC-

CHO and 100 equivalents for 10MC-CHO) was added dropwise into the solution. After

12 hours, the reaction was quenched with water, and extracted with diethyl ester. After

drying the combined organic phase over sodium sulfate, the solvents were then removed

to afford the crude alcohol product 8MC-OH or 10MC-OH. Without further purification,

these two compounds were dissolved in 20 mL of dry DCM treated with 0.5 mL of

BF3.Et2O. The reaction color changed immediately, and the products 8MC-H and 10MC-

H with fluorescence were generated. After three hours, the reaction was quenched with

water. The mixture was extracted with DCM followed by dried over anhydrous sodium

sulfate. After solvent was removed and the residue was purified with silica gel column

chromatography (Hexane: DCM = 3: 2, v/v) to afford 8MC-H and 10MC-H as white solids

in 57% and 63% yield, respectively. The structures of both compounds were confirmed by

HR MS (Figure S3 and Figure S4) and 2D 1H-1H NOESY NMR measurements (Figure S5

and Figure S6). The purity was further confirmed by recycling analytical GPC (Figures S7-

S8).

8MC-H. 1H NMR (CD2Cl2, 400 MHz): δ ppm 8.95-8.78 (m, 8H), 6.90 (s, 16H), 6.73-6.40

(m, 8H), 5.78-54 (m, 8H), 2.54-2.47 (m, 24H), 2.21-2.07 (m, 24H), 1.76 (s, 8H), 1.28 (s,

8H), 0.70-0.50 (m, 8H). 13C NMR (CD2Cl2, 100 MHz): δ ppm 148.60, 141.39, 138.37,

138.02, 136.71, 134.15, 130.89, 129.07, 120.86, 122.12, 51.48, 21.98, 21.79, 20.93. HRMS

(APCI, m/z): [(M+H)+] calcd for C128H113, 1649.8837; found, 1649.8854.

10MC-H. 1H NMR (CD2Cl2, 400 MHz): δ ppm 8.62 (s, 10H), 6.88 (t, J = 11.6 Hz, 20H),

6.47 (s, 10H), 5.61-5.39 (m, 10H), 2.64-2.43 (m, 30H), 2.14 (s, 30H), 1.18-1.02 (m,

30H).13C NMR (CD2Cl2, 100 MHz): δ ppm 147.54, 140.21, 137.79, 137.37, 136.22,

134.19, 130.25, 128.73, 119.84, 119.49, 111.24, 111.06. HRMS (APCI, m/z): [(M+H)+]

calcd for C160H140, 2061.0950; found, 2061.0947.

Compounds 8MC-M and 10MC-M. 8MC-H (15 mg, 0.0091 mmol) or 10MC-H (15 mg,

0.0073 mmol) was dissolved in 15 mL of anhydrous DCM under argon atmosphere. 2,3-

S5

Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (8 equivalents for 8MC-H, 10 equivalents

for 10MC-H) was added to the solution in portion and the progress of the reaction was

monitored by MALDI-TOF mass spectra (Figures S9-S10). For both reactions, the color

changed quickly from colorless to dark green (8MC-M) and dark blue (10MC-M). After

reacting for 45 mins (for 8MC-M) or 15 mins (for 10MC-M), the solvent was removed

under vacuum. The crude product was purified by flash column chromatography (10%

trimethylamine deactivated silica gel, DCM as the eluent) followed by precipitation into

acetonitrile to afford the final products of 8MC-M and 10MC-M in nearly quantitative

yield. The purity was further confirmed by recycling analytical GPC (Figures S13-S14).

8MC-M. This compound is reasonably stable at ambient air and light condition in both

solution and in solid state. The structure of 8MC-M was confirmed by HR MS (Figure

S11), VT 1H NMR spectrum (Figure 2A, full range spectrum in Figure S15, and relative

integral intensity in Figures S16-17), 2D 1H-1H ROESY NMR spectrum (Figure S18), and

a preliminary X-ray crystallographic analysis (Figure S19). 1H NMR (THF-d8, 233 K, 500

MHz): δ ppm 11.37 (s, proton “a”), 6.85 (m, proton “c”), 1.28 (s, proton “e”), 0.87 (s,

proton “d”), -12.08 (s, proton “b”). The signals for protons “a-c” are very weak due to

exchange with the thermally populated triplet species, which limits the 2D NOESY NMR

analysis as we all as 13C NMR spectral measurement. HR MS [APCI, m/z (z =1), [(M+H)+]

calculated for C128H104, 1640.8133; found, 1640.8124.

10MC-M. This compound is reasonably stable at ambient air and light condition in both

solution and in solid state. The 1H NMR spectrum of 10MC-M was significantly broadened

due to its triplet ground state and only broadened resonances for methyl groups can be

observed at various temperatures. Its structure was confirmed by HR MS (Figure S12) and

preliminary X-ray crystallographic analysis (Figure S20). HR MS [ESI, m/z (z=2),

(M+H)+] calculated for C160H130, 1025.5081; found, 1025.5083.

1.3. Additional spectra and figures

Figure S1. Four and the only four possible resonance structures of 8MC and 10MC in

their closed-shell forms.

S6

Figure S2. MALDI-TOF mass spectrum for the reaction mixture of Suzuki coupling

reaction mediated macrocyclization. In addition to the [4+4] (8MC-CHO, m/z = 832.4

g/mol) and [5+5] (10MC-CHO, m/z = 1040.5 g/mol) products, the [3+3] (m/z = 624.1

g/mol) and [6+6] (m/z = 1248.7 g/mol) products were also detected. However, they could

not be isolated by recycling GPC.

Figure S3. HR-APCI [m/z (z = 1), (M+1)+] mass spectrum of 8MC-H.

S7

Figure S4. HR-APCI [m/z (z = 1), (M+1)+] mass spectrum of 10MC-H.

S8

Figure S5. 1H-1H NOESY NMR spectrum of 8MC-H in CD2Cl2 (500 MHz). Due to the

existence of various isomers and the bowl-shaped structure, all the protons were split into

multiple peaks. The assignment was based on the through space interaction between the

neighboring protons. The integration was in agreement with the theoretical prediction.

ad

b cf e g g g

g

g

gef

c

bd

a

d, e

d, f c, f

d, f d, eb, e

c, f

S9

Figure S6. 1H-1H NOESY NMR spectrum of 10MC-H in CD2Cl2 (500 MHz). Due to the

existence of various isomers, some of the protons were split into multiple peaks. The

assignment was based on the through space interaction between the neighboring protons.

The integration was in agreement with the theoretical prediction.

ad

b ce f g

g

fe

c

b

d

a

d, f

d, e

c, d

c, e

c, d

c, e

d, e d, f

b, f

S10

Figure S7. Recycling GPC curves of 8MC-H in the first 14 cycles. Shimazu GPC column

K802 (8.0mm id x 30cm), SPD-20AV UV-Vis spectrophotometric detector (210 nm), and

chloroform as eluent.

Figure S8. Recycling GPC curves of 10MC-H in the first 13 cycles. Shimazu GPC column

K802 (8.0mm id x 30cm), SPD-20AV UV-Vis spectrophotometric detector (red: 210 nm;

blue: 280 nm), and chloroform as eluent.

S11

Figure S9. Oxidative dehydrogenation process for 8MC-H (a) and 10MC-H (b) monitored

by MALDI-TOF MS after addition of DDQ in anhydrous DCM. They were fully converted

to final products 8MC-M and 10MC-M in 45 and 15 minutes, respectively.

Figure S10. MALDI-TOF mass spectra of 8MC-M (a) and 10MC-M (b). Inset is a

comparison between calculated and observed isotopic distributions.

1640 1650

0

50

100

150

200

250

300

Inte

ns

ity

(a

.u.)

m/z

1635 1640 1645 1650 16550

100

200

300

400

500

Inte

ns

ity

(a

.u.)

m/z

1640 1650

0

200

400

600

800

1000

1200

Inte

ns

ity

(a

.u.)

m/z

2040 2050 2060 2070

0

200

400

600

800

1000

Inte

ns

ity

(a

.u.)

m/z

2040 2045 2050 2055 2060 2065 2070

0

50

100

150

200

250

Inte

ns

ity

(a

.u.)

m/z

1648.1

1649.11650.1

1651.1

1652.1

1642.91641.9

1640.9

1643.8

1644.81645.91646.8

1647.81649.9

1640.8

1649.9

1641.8

1642.8

1643.8

1644.8

2059.5

2060.5

2061.5

2062.5

2063.5

2064.5

2052.1

2051.1

2053.1

2054.1

2055.1

2056.1

10MC-H

10MC-M

8MC-H

8MC-M

15 min

45 min 15 min

(a) (b)

1639.9

500 1000 1500 2000

0

200

400

600

800

Inte

nsity (

a.u

.)

m/z

8MC-M

1000 1500 2000 2500

0

200

400

Inte

nsity (

a.u

.)

m/z

10MC-M

1640 1645 1650 1655m/z

observed

calculated

2050 2055 2060 2065m/z

observed

calculated

(a) (b)

1641.80 2052.11

S12

Figure S11. HR-APCI [m/z (z = 1), (M+1)+] mass spectrum of 8MC-M.

Figure S12. HR-ESI [m/z (z = 2), (M+H)+] mass spectrum of 10MC-M.

S13

Figure S13. Recycling GPC curves of 8MC-M in the first 3 cycles. Shimazu GPC column

K802 (8.0mm id x 30cm), SPD-20AV UV-Vis spectrophotometric detector (blue: 280 nm;

green: 350 nm; orange: 400 nm), and chloroform as eluent.

Figure S14. Recycling GPC curves of 10MC-M in the first 3 cycles. Shimazu GPC column

K802 (8.0mm id x 30cm), SPD-20AV UV-Vis spectrophotometric detector (red: 210 nm;

green: 350 nm; orange: 400 nm), and chloroform as eluent.

S14

Figure S15. Full-range 1H NMR spectrum of 8MC-M in THF-d8 at 233 K. The signals for

protons “a”-“c” are very weak due to exchange with thermally populated triplet species

and thus these signals are magnified. The stars indicate the residue solvent peaks.

Figure S16. The relative integral intensity of protons “a” and “b” in the 1H NMR

spectrum of 8MC-M at 233 K.

a

ab

b

c

c

H2O

e

*

* *d

S15

Figure S17. The relative integrals of protons “e” and “d” in 1H NMR spectrum of 8MC-

M at 233 K, showing a nearly 2: 1 ratio. The stars indicate the residue solvent peaks.

edH2O

**

S16

Figure S18. 2D 1H-1H ROESY NMR spectrum of 8MC-M in THF-d8 at 233 K. (A) Full-

range spectrum; (B) magnified narrow-range spectrum showing the interaction between

protons “c” with protons “d” and “e”; (C) magnified narrow-range spectrum showing the

interaction between protons “a” with protons “e”.

S17

Figure S19. X-ray crystallographic structure (left: top-view; right: side-view) of 8MC-M.

The backbone is clearly confirmed and shows a bowl-shaped geometry, in agreement with

DFT calculation. However, due to the low quality of the data (weak diffraction and

existence of disordered solvents), we could not do bond length analysis.

Figure S20. X-ray crystallographic structure (left: top-view; right: side-view) of 10MC-

M. The backbone is clearly confirmed and nearly planar, in agreement with DFT

calculation. However, due to the low quality of the data (weak diffraction and existence of

disordered solvents), we could not do bond length analysis.

S18

Figure S21. (a) Optimized (UB3LYP/6-31G(d,p)) geometry of 8MC-M in the singlet

diradical ground state with atom labels (see Cartesian coordinates in Appendix). (b)

Calculated (restricted) 1H NMR spectrum (B3LYP/6-31G(d,p)-GIAO) based on the

optimized geometry. (c) Chemical structure and labeling of 8MC-M, with the bowl

pointing from the inner hub to the outer rim through the paper. Protons e and c point to the

concave side, while protons e’ and c’ point to the convex side. Calculations predict that

proton a will appear at very low field (δ = +13.0 ppm), while proton b will appear in very

high field (δ = -20.2 ppm), which is in agreement with the experimental observation (Figure

2A in the main manuscript). At the same time, all the protons e and c at the concave side

will appear at the higher field than those (e’, c’) at the convex side due to the shielding/de-

shielding effect. It should be pointed out that the calculation was based on the single

optimized geometry and the chemical shifts for the protons on the mesityl groups are very

sensitive to the geometry and local environment and what we measured are the averaged

peaks. So the most useful information from this calculation is the relative position of the

protons “a” and “b”, rather than the absolute values.

S19

We also optimized 8MC-M at the (restricted and unrestricted) KMLYP/6-31G(d,p) level

of theory. Based on the optimized geometries (see Cartesian coordinates in Appendix),

relative 1H chemical shifts were calculated as:

𝛿𝑐𝑎𝑙𝑐𝑥 = 𝜎𝑟𝑒𝑓 − 𝜎𝑥

where 𝜎𝑟𝑒𝑓 and 𝜎𝑥 are the NMR isotropic magnetic shielding values for the reference

(TMS) and the X proton of 8MC-M, respectively, calculated at (restricted) KMLYP/6-

311+G(2d,p)-GIAO method. In agreement with previous results, i.e. experimental and

B3LYP calculations, a and b protons appear at very low (δ = 14.80 – 14.78 ppm) and very

high field (δ = -24.06 - -24.10 ppm), respectively (Figures S22-S23 and Table S1).

Figure S22. Calculated 1H NMR spectrum of 8MC-M by KMLYP/6-31G(d,p)-GIAO

method obtained for the (restricted) KMLYP/6-31G(d,p) geometry.

Figure S23. Calculated 1H NMR spectrum of 8MC-M by KMLYP/6-31G(d,p)-GIAO

method obtained for the (unrestricted) KMLYP/6-31G(d,p) geometry.

S20

Table S1. Relative 1H shifts (in ppm) for 8MC-M computed at the (restricted) KMLYP/6-

31G(d,p)-GIAO level for the geometries optimized at the restricted and unrestricted

KMLYP/6-31G(d,p) level. Proton labels correspond to Figure S21 (c). Displacements for

d, e and e’ are given as an averaged single value. 𝜎𝑇𝑀𝑆 = 31.12 𝑝𝑝𝑚.

proton (U)KMLYP (R)KMLYP Experiment

a 11.75 14.36 11.73

b -18.60 -22.74 -12.46

c 6.11 6.63

c’ 7.98 9.01

d 1.94 1.75 3.23

e -2.69 -4.43 1.27

e’ 5.18 5.64 0.89

Figure S24. Bond labels employed in the comparison between restricted/unrestricted

KMLYP/6-31G(d,p) geometries (Table S2).

Table S2. Comparison between structural parameters of 8MC-M obtained at the restricted

and unrestricted KMLYP/6-31G(d,p) computational level. All distances are in Angstroms.

Bond labels are indicated in Figures S24.

bond (R)KMLYP (U)KMLYP

A 1.422 1.410

B 1.408 1.389

C 1.460 1.438

D 1.424 1.404

E 1.388 1.370

S21

The validity of the employed basis set 6-31G(d,p) in the computation of proton relative

shifts has been tested by comparing the results with the larger basis set 6-311+G(2d,p)

(Figure S25). The results indicate no major differences with the values obtained with 6-

31G(d,p).

Figure S25. Calculated 1H NMR spectrum of 8MC-M by KMLYP/6-311+G(2d,p)-GIAO

method obtained for the (restricted) KMLYP/6-31G(d,p) geometry.

Calculations of relative 1H shifts have been done with Gaussian 09 rev D.01. The KMLYP

functional is requested with the following keyword combination:

BLYP IOp(3/76=1000005570) IOp(3/77=0000004430) IOp(3/78=0448010000)

S22

Figure S26. VT ESR spectra of 8MC-M (a) and 10MC-M (b) in DCM (173K to118 K).

Figure S27. Measured (dot) and fitted (red plot) χMT-T curve in the SQUID measurement

for the powder of 10MC-M.

327 328 329 330 331-200

-150

-100

-50

0

50

100

150

200

Inte

nsit

y

Field (mT)

-100 oC

-110 oC

-120 oC

-130 oC

-140 oC

-150 oC

-155 oC

326 327 328 329 330 331-4000

-3000

-2000

-1000

0

1000

2000

3000

4000

Inte

nsit

y

Field (mT)

-100 oC

-110 oC

-120 oC

-130 oC

-140 oC

-150 oC

-155 oC

173 K

163 K

153 K

143 K

133 K

123 K

118 K

173 K

163 K

153 K

143 K

133 K

123 K

118 K

S23

Figure S28. Transient absorption spectra for 8MC-M (a) and 10MC-M (c) recorded in

toluene and decay profiles for 8MC-M (b) and 10MC-M (d).

2. Theoretical calculations

All computational results presented have been obtained for a molecular model where

the mesityl substituents are replaced by hydrogen substituents (8MC and 10MC). The

perpendicular disposition of the side aryl rings with respect to macrocycle suggests that

they have a minor impact in the electronic structure properties and justifies not considering

them in the computational modeling. Molecular geometries have been obtained at the

UB3LYP/6-31G(d,p) level with Gaussian 09 package1. The radical nature of the electronic

ground state and transition energies to higher states were calculated using the restricted

active space spin-flip method (RAS-SF) with Q-Chem 4.3 package2. In 8MC (10MC) we

used a spin 9-et (11-et) ROHF configuration as reference, with 8 (10) electrons in 8 (10)

orbitals as the RAS2 space and a quadruple (quintuple) spin-flip excitation operator. The

radical character degree of the ground state singlet was estimated by the number of

unpaired electrons (NU) according to equation 1, where {ni} are the natural occupation

numbers from the one-particle density matrix3-4.

i

iU nabsN )1(1 (1)

The calculated occupation numbers of HONO-i and LUNO+i (i = 0, 1, 2) can be used

as the multiple radical character indices yi calculated by using equation 25:

𝑦𝑖 =1

2(2 − 𝑛𝐻𝑂𝑁𝑂−𝑖 + 𝑛𝐿𝑈𝑁𝑂+𝑖) (2)

450 600 750 900 1050 1200 1350

-4

-3

-2

-1

0

1

8MC-M in toluene

mA

Wavelength (nm)

Time / ps

-0.5

0.3

0.4

0.5

0.6

1.0

3.0

5.0

10.0

20.0

25.0

450 600 750 900 1050 1200 1350

-15

-10

-5

0

5

m

A

Wavelength (nm)

Time / ps

-0.5

0.3

0.4

0.5

0.6

1.0

2.0

5.0

10.0

20.0

25.0

10MC-M in toluene

0 5 10 15 20 25 30 35 40

-25

-20

-15

-10

-5

0

m

A

Time / ps

pump = 700 nm

probe = 600 nm

= 0.3 and 8 ps

0 5 10 15 20 25 30 35 40

-20

-15

-10

-5

0

m

ATime / ps

pump = 700 nm

probe = 700 nm

= 0.2 and 6 ps

S24

NICS values were calculated using the standard GIAO (GIAO=NMR)6 at the level of

(U)B3LYP/6-31G(d,p). To obtain best NICS aromaticity index for 8MC and 10MC,

NICSzz values were selected.7 The iso-chemical shielding surface (ICSS)8-10 calculations

were carried out to analyze two-dimensional nucleus induced chemical shifts (2D-NICSzz)

depending on various planes. Plotting the ICSS having same scale allows us to compare

the aromaticity between the singlet and triplet state of 8MC and 10MC. Anisotropy of the

induced current density (ACID) plots (iso-value = 0.04) were calculated at (U)B3LYP/6-

31G(d,p) level by using the method developed by Herges.11 To devoid σ-bond effect, the

additional option (NMR=CSGT, IOp(10/93) = 2) was used to read in wanted p-orbitals.

The p-orbitals were classified with the analysis of molecular orbital (MO) calculations

using the optimized structures of 8MC and 10MC in the singlet and triplet state.

Our calculations show that the lowest state for the 8MC corresponds to a spin singlet

with C8v symmetry (Figure S26), although C2v and C4v singlets are computed at practically

the same energy. The lowest 10MC state is a spin triplet with D2h symmetry (Figure S26).

It is worth noting that the ring tension in 8MC strongly suppresses molecular planarity

favoring Cnv molecular symmetries. The bowl-to-bowl inversion barrier of 8MC via S-

shaped TS (Ci symmetry) was found at 29.3 kcal/mol (Figure S27). Frequency calculations

for the S-shaped structure confirms that it indeed corresponds to a critical point on the

potential energy surface of 8MC, with a vibrational mode with an imaginary frequency,

(freq = 47.5i cm-1) and a very flat mode (freq ~ 0), corresponding to symmetric and

antisymmetric vibrations out of the “molecular plane”, connecting S-shape with the C8v

(minimum) and D8h (planar) geometries, respectively. The planar structure lies at 31.5

kcal/mol with respect to the minimum (C8v) geometry (Figure S27).

Both molecules exhibit a fairly large amount of electronic states within a rather small

energy gap with respect to the electronic ground state (Figure S28 and Table S1). The

natural orbitals and occupancies for the lowest states of 8MC and 10MC molecules, i.e.

spin singlet and triplet, respectively are shown in Figure S30 and Figure S31, respectively,

and some indices quantifying the radical character are shown in Table S2.

Both 1H NMR measurements and ACID calculations of 8MC indicate that the ground

state singlet exhibits global aromaticity. Moreover, ACID and current plots (Figure 3A in

the main manuscript and Figure S33) indicate that such aromaticity can be understood or

approximated as the sum of two clockwise currents on each annulene ring (in and out). On

the other hand, the two annulene rings hold 4n electrons (24 πe, 32 πe), hence in the ground

state singlet we would expect counter-clockwise ring currents. Therefore, we consider two

alternative electronic structures as the source for global aromaticity in 8MC (ground state

singlet): (1) One annulene gives two electrons to the other one (Hückel's rule); (2) each

annulene holds a "triplet" (diradical) character (Baird's rule).

To identify which is the most plausible explanation we perform constrained DFT (C-

DFT) calculations by imposing restrictions in the inner and outer annulene rings of 8MC.

The idea is to use energy arguments to quantify the relative stability of these different

conformations and identify which might be contributing to the ground state wave function.

We call them diabatic states in the sense that they are well characterized by the charge/spin

S25

within each of the two annulenes. The "true" (adiabatic) lowest singlet (or triplet) state is

expected to be a combination of the lowest diabatic states.

The relative energies in Figure S32 for the 8MC singlet indicate that SS, TT, 1+/1- and

1-/1+ are much lower in energy than the 2-/2+ and 2+/2- states and it is unlikely that the

dianion/dication density-constrained states participate to the ground state wave function.

Hence, our calculations point towards option 2: the global aromaticity of the singlet ground

state of 8MC can be seen due to the "triplet(in)-triplet(out)" (or diradical-diradical)

character of the ground state, that is two triplets coupled as a singlet. These results can be

rationalized due to the large polyradical character in 8MC and to the diradicaloid character

in each in/out annulenes. This result is in agreement with the number of unpaired electrons

computed at the RAS-SF level (NU = 4.85 in Table S2) and with ACID calculations for the

entire molecule and for the in/out models (Figure 3A in main manuscript), and corresponds

to the application of Baird's rule to the inner and outer annulenes.

Similarly, we can rationalize that the aromaticity in 8MC triplet corresponds to mainly

having a singlet (in)-triplet(out) state (ST), which is lower in energy than the TS

configuration (Figure S32). The inner ring is anti-aromatic (Hückel’s rule) while the outer

ring is aromatic (Baird’s rule) (Figures S33-S34). The two states of 10MC (30 πe, 40 πe)

can be also rationalized with C-DFT calculations. Again, the 2-/2+ and 2+/2- states are

much higher in energy in both 10MC singlet and triplet states (Figure S32). The lowest

contribution in the 10MC ground state triplet is the ST state, with both the inner ring and

outer rings are aromatic, by following Hückel’s rule and Baird’s rule, respectively (Figure

3C and Figure S35). The first singlet excited state of 10MC have either TT or SS states

with close energy, and in both states, the cancelation effect of the inner ring and outer rings

(aromaticity vs. anti-aromaticity) leads to a non-aromatic character (Figure S36).

For comparison, similar calculations were conducted for the hydrogenated analogues of

8MC and 10MC, that is, 8MC-16H and 10MC-20H, in which eight and ten protons are

added to the radical centers in the cyclcopenta-ring, respectively (Figure S39A). The

calculated ACID plots and NICSzz maps (Figure S39B-E) clearly show the localized

aromatic character at each benzene ring, without any global aromaticity.

To conclude, despite the rather complicated electronic structure nature of lowest singlet

and triplet states of the two studied macrocycles, the global aromaticity in 8MC (singlet)

can be qualitatively seen as a result of some TT character in the ground state wave function,

and not from dianion/dication contributions. Similar arguments can be used for 10MC.

S26

Figure S29. Lowest conformers for 8MC (bowl-shaped) and 10MC (planar) molecules.

Figure S30. Inversion energy profile between C8v structures 8MC through a D8h planar

and a S-shape structures. Energies computed at the B3LYP/6-31G(d) level.

S27

Figure S31. Vertical excitation energies (in kcal/mol) computed at the RAS-SF/6-31G(d)

level for the lowest electronic states of 8MC (C8v) and 10MC (D2h).

S28

Table S3. A comparison of the calculated vertical excitation energies (in kcal/mol) of 8MC

and 10MC by RAS-SF/6-31G(d) and UB3LYP/6-31G(d,p) method. Spin-unrestricted DFT

energies appear slightly higher than RAS-SF results. Moreover, the strong

multiconfigurational character of 8MC and 10MC molecules advises the use of an

electronic structure approach able to deal with strong correlations. Therefore, in this case,

we consider RAS-SF energy gaps to be more reliable than the UB3LYP counterparts.

Relative

Energy

(kcal/mol)

RAS-SF/6-31G(d) UB3LYP/6-31G(d,p)

8MC 10MC 8MC 10MC

singlet S1 0.0 0.4 0 1.2

S2 3.5 1.1

S3 4.3 2.7

S4 4.8 2.9

S5 5.1 3.8

S6 5.1 -

S7 6.9 -

S8 7.6 -

S9 9.3 -

S10 9.6 -

triplet T1 2.7 0.0 3.6 3.8

T2 3.2 1.0

T3 3.2 1.0

T4 4.9 2.1

T5 4.9 2.6

T6 5.7 -

T7 5.7 -

T8 6.4 -

quintet Q1 5.2 1.5 16.2 0.0

Q2 7.0 2.8

Q3 7.2 3.0

Q4 7.3 3.9

Q5 7.6 5.2

Q6 8.4

Q7 10.1

Q8 10.5

septet SE1 11.6 6.7 23.3 16.5

SE2 12.5 8.9

SE3 12.7 12.9

nonet NON1 20.6 12.9 34.8 27.7

NON2 - 15.2

NON3 - 20.7

11-et 11-et1 - 22.8 - 50.3

S29

Figure S32. Calculated (UB3LYP/6-31G(d,p)) spin density (α spin-β spin) distribution

maps of 8MC and 10MC at their different spin states (iso-value = 0.002).

S30

Figure S33. Frontier natural orbitals and electronic occupancies for the lowest state (open-

shell singlet) of 8MC computed at the RAS-SF/6-31G(d) level.

S31

Figure S34. Frontier natural orbitals and electronic occupancies for the lowest state

(triplet) of 10MC computed at the RAS-SF/6-31G(d) level.

Table S4. Calculated radical indices yi, i = 0, 1, 2, 3, 4, number of unpaired electrons

(NU) and singlet-triplet energy gaps (ΔEST in kcal/mol) at the RAS-SF/6-31G(d) level.

8MC (C8v) 10MC (D2h)

Singlet Triplet

y0 0.79 1.00 1.00

y1 0.56 0.92 0.97

y2 0.56 0.56 0.55

y3 0.45 0.53 0.50

y4 - 0.48 0.46

NU 4.85 7.08 7.04

ΔEST -2.7 +0.4

S32

Figure S35. State energy diagram for the diabatic states of 8MC and 10MC molecules

computed with C-DFT. All energies are given with respect to the lowest singlet or triplet

state. State labels correspond to the restriction on inner/outer annulene rings, respectively.

SS: singlet-singlet, TT: triplet-triplet; 1-/1+: anion-cation; 2-/2+: dianion-dication.

S33

Figure S36. Magnified ACID plots for 8MC. (A) Magnified ACID plot for 8MC in its

singlet (TT) state. (B) Magnified ACID plot for 8MC in its first triplet (ST) excited state.

Figure S37. ACID plots and 2D NICS map. (A) ACID plots of the individual inner/outer

rings and 8MC in the first triplet excited state. (B) 2D NICSzz map of 8MC in the first

triplet excited state. The arrows along the inner/outer rings indicate a clockwise

(diamagnetic) or a counter-clockwise (paramagnetic) current flow, and the arrows in the

rings show the alignment of the frontier two or four π electrons.

8MC-singlet (TT) 8MC-triplet (ST)

8MC-out-Triplet

+

32 πe24 πe

8MC-in-Singlet

-7.5 -5.0 -2.5 0.0 2.5 5.0 7.5

-3.0

-1.5

0.0

1.5

3.0

-7.5

-5.0

-2.5

0.0

2.5

5.0

7.5

Y-a

xis

(Å

)

60.000

30.000

0.000

-30.000

-60.000

X-axis (Å)

Z-a

xis

(Å

)

+

8MC-Triplet (ST)

A B

NICSzz(0) = 9.96 ppm

S34

Figure S38. Magnified ACID plots for 10MC in its triplet ground state.

Figure S39. ACID plots and 2D NICS map. (A) ACID plots of the individual inner/outer

rings and 10MC in the first singlet excited state. (B) 2D NICSzz map of 10MC in the first

singlet excited state showing non-aromatic character. The TT and SS states have a similar

energy, and due to the cancelation effect (aromaticity vs anti-aromaticity) between the inner

and outer rings in both cases, the molecule is non-aromatic. The arrows along the

inner/outer rings indicate a clockwise (diamagnetic) or a counter-clockwise (paramagnetic)

current flow, and the arrows in the rings show the alignment of the frontier two or four π

electrons.

30 πe

+OR

10MC-out-Triplet

10MC-in-Singlet

10MC-in-Triplet

10MC-out-Singlet

SS

TT

+

+

40 πe

NICSzz(0) = -6.17 ppm

-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0

-10.0

-7.5

-5.0

-2.5

0.0

2.5

5.0

7.5

10.0

X-axis (Å)

Y-a

xis

(Å

)Z

-axis

(Å

)

-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0

-2-1012

100.000

-50.000

0.000

50.000

-100.000

+

S35

The expected contributions of individual rings (inner and outer) to the molecular

aromaticity for singlet and triplet states can be obtained following the Hückel’s and Baird’s

rules, respectively. On the other hand, there isn’t a well-established rule for aromaticity on

doublet states, i.e. rings with +1 or -1 charge. Mandado et al. suggested an “expanded

Baird’s rule” for radical systems to evaluate aromaticity as the sum of separate

contributions from α and β π-electrons, respectively.12 Following these rules, in Table S3

we estimate contributions to the aromaticity.

Table S5. Contributions to the global aromaticity from α and β π-electrons for each diabatic

state of inner (_in) and outer (_out) rings of 8MC and 10MC molecules. S = singlet (close-

sell), D = doublet, T = triplet, A = aromatic, AA = antiaromatic, NA = no aromatic

(cancelation between α and β contributions).

ring

model

spin

multiplicity

charge α-elec β-elec global

8MC_in S 0 12 (AA) 12 (AA) AA

8MC_in T 0 13 (A) 11 (A) A

8MC_in D -1 13 (A) 12 (AA) NA

8MC_in D +1 12 (AA) 11 (A) NA

8MC_in S -2 13(A) 13(A) A

8MC_in S +2 11(A) 11(A) A

8MC_out S 0 16 (AA) 16 (AA) AA

8MC_out T 0 17 (A) 15 (A) A

8MC_out D -1 17 (A) 16 (AA) NA

8MC_out D +1 16 (AA) 15 (A) NA

8MC_out S -2 17(A) 17(A) A

8MC_out S +2 15(A) 15(A) A

10MC_in S 0 15 (A) 15 (A) A

10MC_in T 0 16 (AA) 14 (AA) AA

10MC_in D -1 16 (AA) 15 (A) NA

10MC_in D +1 15 (A) 14 (AA) NA

10MC_in S -2 16(AA) 16(AA) AA

10MC_in S +2 14(AA) 14(AA) AA

10MC_out S 0 20 (AA) 20 (AA) AA

10MC_out T 0 21 (A) 19 (A) A

10MC_out D -1 21 (A) 20 (AA) NA

10MC_out D +1 20 (AA) 19 (A) NA

10MC_out S -2 21(A) 21(A) A

10MC_out S +2 19(A) 19(A) A

In order to further explore the contributions of +1/-1 and -1/+1 configurations to the global

aromaticity, we investigated the anisotropy of the current-induced density (ACID) plots of

±1 annulene inner and outer model rings. Charged (±1) inner rings of 8MC can be

classified as antiaromatic, since they holds a counter-clockwise current. While, the ACID

of ionic outer ring of 8MC seems to be disconnected, i.e., without a continuous current

flow along the ring. Inner/outer rings of 10MC show counter-clockwise (antiaromatic) and

clockwise (aromatic) current flows, respectively (Figure S37).

S36

Figure S40. ACID plots of ionic fragments of 8MC (top) and 10MC (bottom).

S37

Figure S41. Calculated bond lengths (in Å) and HOMA values of each individual rings for

8MC and 10MC in their ground state and the first excited state.

S38

Figure S42. ACID plots and 2D NICS maps of 8MC-16H and 10MC-20H. (A)

Chemical structure of 8MC-16H and 10MC-20H. ACID plots for 8MC-16H (B) and

10MC-20H (D) show localized aromaticity on each benzene ring. 2D NICSzz maps of

8MC-16H (C) and 10MC-20H (E) show no-aromatic character at the center of

macrocycles.

-7.5 -5.0 -2.5 0.0 2.5 5.0 7.5

-2

-1

0

1

2

Y-a

xis

(Å

)

-7.5

-5.0

-2.5

0.0

2.5

5.0

7.5

60.000

30.000

0.000

-30.000

-60.000

X-axis (Å)

Z-a

xis

(Å

)

-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0

-10.0

-7.5

-5.0

-2.5

0.0

2.5

5.0

7.5

10.0

X-axis (Å)

Y-a

xis

(Å

)Z

-axis

(Å

)

-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0-3-2-10123

100.000

-50.000

0.000

50.000

-100.000



S39

3. X-ray crystallographic data

Table S6. Crystallographic data and structure refinement for 8MC-CHO. CCDC

number: 1559806.

Empirical formula C66 H51 N O10

Formula weight 1018.08

Temperature 100(2) K

Wavelength 1.54178 Å

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 11.2862(5) Å a= 101.119(2)°.

b = 12.4963(5) Å b= 99.809(2)°.

c = 20.0553(8) Å g = 108.339(2)°.

Volume 2552.12(19) Å3

Z 2

Density (calculated) 1.325 Mg/m3

Absorption coefficient 0.719 mm-1

F(000) 1068

Crystal size 0.312 x 0.132 x 0.099 mm3

Theta range for data collection 2.318 to 70.067°.

Index ranges -13<=h<=13, -15<=k<=15, -23<=l<=24

Reflections collected 34654

Independent reflections 9596 [R(int) = 0.0356]

Completeness to theta = 67.679° 99.1 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.7536 and 0.6518

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 9596 / 707 / 861

S40

Goodness-of-fit on F2 1.058

Final R indices [I>2sigma(I)] R1 = 0.0700, wR2 = 0.1984

R indices (all data) R1 = 0.0768, wR2 = 0.2067

Extinction coefficient n/a

Largest diff. peak and hole 0.964 and -0.966 e.Å-3

Table S7. Crystallographic data and structure refinement for 10MC-CHO. CCDC

number: 1559833.

Empirical formula C70 H40 O10




Crystal system Monoclinic

Space group C2/m

Unit cell dimensions a = 27.067(2) Å a= 90°.

b = 23.017(2) Å b= 122.082(5)°.

c = 15.3850(12) Å g = 90°.

Volume 8121.0(12) Å3

Z 4



F(000) 2160



Index ranges -32<=h<=32, -27<=k<=26, -16<=l<=18






S41








X-ray data of 8MC-M were measured at low temp of 100K with a Bruker D8 Venture

diffractometer equipped with a four circles Kappa goniometer and Photon II detector. A

monochromated Cu Kα radiation (λ = 1.54187 Å) was used for the measurement. The

structure was solved by using direct methods.13 Structure refinements were carried out by

using SHELXL-2014/7 program.14 CCDC number: 1574873 contains supplementary

crystallographic data. These data can be obtained free of charge from the Cambridge

Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Single crystal of 8MC-M was obtained through slow diffusion of acetonitrile to the

chlorobenzene solution by layering method. The crystals were very thin long needles and

contained many severely disordered solvent molecules in the cavity. They gave only weak

diffractions at high two theta angles. However, the main skeletal structure was solved. The

contributions to the scattering arising from the presence of the disordered solvents in

the crystal were removed by use of the utility SQUEEZE in the PLATON software

package.15

Table S8. Crystallographic data and structure refinement for 8MC-M.

Empirical formula C128 H104




Crystal system Tetragonal

Space group P4/ncc


b = 30.4484(16) Å b= 90°.

c = 13.7537(8) Å g = 90°.

Volume 12751.1(15) Å3

Z 4



F(000) 3488



Index ranges -32<=h<=32, -32<=k<=33, -14<=l<=14





http://www.ccdc.cam.ac.uk/data_request/cif

S42









X-ray data of 10MC-M were taken at 93K with a Rigaku XtaLAB P200 diffractometer by

using graphite monochromated Cu K radiation ( = 1.54187 Å) (We thank Professor

Atsuhiro Osuka for sharing his equipment!). The structure was solved by using direct

methods.12 Structure refinements were carried out by using SHELXL-2014/7 program.13

CCDC number: 1559835 contains supplementary crystallographic data. These data can be

obtained free of charge from the Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

Single crystal of 10MC-M was obtained through slow diffusion of acetonitrile to the

chlorobenzene solution. Since the crystals were tiny and contained many severely

disordered solvent molecules in the cavity, they gave only weak diffractions. However,

these are not significant concern for the main skeletal structure. The contributions to the

scattering arising from the presence of the disordered solvents in the crystal were removed

by use of the utility SQUEEZE in the PLATON software package.14 The carbon-carbon

bonds were appropriately restrained by DFIX, SADI and DANG instruments during

refinement.

Table S9. Crystallographic data and structure refinement for 10MC-M.

Empirical formula C160 H130




Crystal system Orthorhombic

Space group Imm2


b = 8.57(3) Å b= 90°.

c = 31.30(12) Å g = 90°.

Volume 11563(70) Å3

Z 2



F(000) 2180



Index ranges -32<=h<=32, -6<=k<=6, -23<=l<=23



S43









Absolute structure parameter 0.5



4. Additional NMR and mass spectra of intermediate compounds

Figure S43. 1H NMR spectrum of 8MC-CHO in CDCl3 (500 MHz).

ab

c

de

e

f

a

b e cdf

S44

Figure S44. 13C NMR spectrum of 8MC-CHO in CDCl3 (125 MHz).

Figure S45. 1H NMR spectrum of 10MC-CHO in CDCl3 (400 MHz).

a

b

cd

e

e

f

a

bd

ecf

S45

Figure S46. 13C NMR spectrum of 10MC-CHO in CDCl3 (100 MHz).

Figure S47. 1H NMR spectrum of 8MC-H in CD2Cl2 (400 MHz).

a

d

b c

f e

ggg

a

bc

dd

ef

g

S46

Figure S48. 13C NMR spectrum of 8MC-H in CD2Cl2 (100 MHz).

Figure S49. 1H NMR spectrum of 10MC-H in CD2Cl2 (400 MHz).

feg

cbda

a

bc

dd

g

ef

S47

Figure S50. 13C NMR spectrum of 10MC-H in CD2Cl2 (100 MHz).

S48

Figure S51. HR-APCI [m/z (z = 1), (M+1)+] mass spectrum of 8MC-CHO.

Figure S52. HR-APCI [m/z (z = 1), (M+1)+] mass spectrum of 10MC-CHO.

S49

5. References

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Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji,

H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G.,

Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida,

M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery Jr., J. A.,

Peralta, J. E., Ogliaro, F., Bearpark, M. J., Heyd, J., Brothers, E. N., Kudin, K. N.,

Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A. P., Burant,

J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, N. J., Klene, M., Knox, J.

E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E.,

Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L.,

Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J.,

Dapprich, S., Daniels, A. D., Farkas, Ö., Foresman, J. B., Ortiz, J. V., Cioslowski, J. &

Fox, D. J. Gaussian 09, Gaussian, Inc., Wallingford, CT, USA, 2009.

[2] Shao, Y., Gan, Z., Epifanovsky, E., Gilbert, A. T. B., Wormit, M., Kussmann, J.,

Lange, A. W., Behn, A., Deng, J., Feng, X., Ghosh, D., Goldey, M., Horn, P. R.,

Jacobson, L. D., Kaliman, I., Khaliullin, R. Z., Kus, T., Landau, A., Liu, J., Proynov, E.

I., Rhee, Y. M., Richard, R. M., Rohrdanz, M. A., Steele, R. P., Sundstrom, E. J.,

Woodcock III, H. L., Zimmerman, P. M., Zuev, D., Albrecht, B., Alguires, E., Austin, B.,

Beran, G. J. O., Bernard, Y. A., Berquist, E., Brandhorst, K., Bravaya, K. B., Brown, S.

T., Casanova, D., Chang, C. -M., Chen, Y., Chien, S. H., Closser, K. D., Crittenden, D.

L., Diedenhofen, M., DiStasio Jr., R. A., Do, H., Dutoi, A. D., Edgar, R. G., Fatehi, S.,

Fusti-Molnar, L., Ghysels, A., Golubeva-Zadorozhnaya, A., Gomes, J., Hanson-Heine,

M. W. D., Harbach, P. H. P., Hauser, A. W., Hohenstein, E. G., Holden, Z. C., Jagau, T. -

C., Ji, H., Kaduk, B., Khistyaev, K., Kim, J., Kim, J., King, R. A., Klunzinger, P.,

Kosenkov, D., Kowalczyk, T., Krauter, C. M., Laog, K. U., Laurent, A., Lawler, K. V.,

Levchenko, S. V., Lin, C. Y., Liu, F., Livshits, E., Lochan, R. C., Luenser, A., Manohar,

P., Manzer, S. F., Mao, S. -P., Mardirossian, N., Marenich, A. V., Maurer, S. A.,

Mayhall, N. J., Oana, C. M., Olivares-Amaya, R., O’Neill, D. P., Parkhill, J. A., Perrine,

T. M., Peverati, R., Pieniazek, P. A., Prociuk, A., Rehn, D. R., Rosta, E., Russ, N. J.,

Sergueev, N., Sharada, S. M., Sharmaa, S., Small, D. W., Sodt, A., Stein, T., Stuck, D.,

Su, Y. -C., Thom, A. J. W., Tsuchimochi, T., Vogt, L., Vydrov, O., Wang, T., Watson,

M. A., Wenzel, J., White, A., Williams, C. F., Vanovschi, V., Yeganeh, S., Yost, S. R.,

You, Z. -Q., Zhang, I. Y., Zhang, X., Zhou, Y., Brooks, B. R., Chan, G. K. L., Chipman,

D. M., Cramer, C. J., Goddard III, W. A., Gordon, M. S., Hehre, W. J., Klamt, A.,

Schaefer III, H. F., Schmidt, M. W., Sherrill, C. D., Truhlar, D. G., Warshel, A., Xu, X.,

Aspuru-Guzik, A., Baer, R., Bell, A. T., Besley, N. A., Chai, J. -D., Dreuw, A., Dunietz,

B. D., Furlani, T. R., Gwaltney, S. R., Hsu, C. -P., Jung, Y., Kong, J., Lambrecht, D. S.,

Liang, W. Z., Ochsenfeld, C., Rassolov, V. A., Slipchenko, L. V., Subotnik, J. E., Van

Voorhis, T., Herbert, J. M., Krylov, A. I., Gill, P. M. W. & Head-Gordon, M. Mol. Phys.

113, 184–215 (2015).

[3] Head-Gordon, M. (2003). Characterizing unpaired electrons from the one-particle

density matrix. Chem. Phys. Lett. 372, 508–511.

S50

[4] Casanova, D., and Head-Gordon, M. (2009). Restricted active space spin-flip

configuration interaction approach: theory, implementation and examples. Phys. Chem.

Chem. Phys. 11, 9779–9790.

[5] Nakano, M., Fukui, H., Minami, T., Yoneda, K., Shigeta, Y., Kishi, R., Champagne,

B., Botek, E., Kubo, T., Ohta, K., and Kamada, K. (2011). (Hyper)polarizability density analysis for open-shell molecular systems based on natural orbitals and occupation numbers. Theor. Chem. Acc. 130, 711–724.

[6] Chen, Z., Wannere, C. S., Corminboeuf, C., Puchta, R., and Schleyer, P. V. R. (2005).

Nucleus-independent chemical shifts (NICS) as an aromaticity criterion. Chem. Rev. 105,

3842–3888.

[7] Fallah-Bagher-Shaidaei, H., Wannere, S. S., Corminboeuf, C., Puchta, R., and Schleyer,

P. V. R. (2006). Which NICS aromaticity index for planar π rings is best?. Org. Lett. 8,

863–866.

[8] Klod, S., and Kleinpeter, E. (2001). Ab initio calculation of the anisotropy effect of

multiple bonds and the ring current effect of arenes—application in conformational and

configurational analysis. J. Chem. Soc., Perkin Trans. 2, 1893–1898.

[9] T. Lu, (2016). Multiwfn Software Manual, Version 3.3.9, Beijing Kein Research

Center for Natural Sciences, Beijing, China.

[10] Lu, T, and Chen, F. (2012). Multiwfn: A multifunctional wavefunction analyzer. J.

Comput. Chem. 33, 580–592.

[11] Geuenich, D., Hess, K., Köhler, F., and Herges, R. (2005). Anisotropy of the

induced current density (ACID), a general method to quantify and visualize electronic

delocalization. Chem. Rev. 105, 3758–3772.

[12] Mandado, M., Graña, A. M., and Pérez-Juste, I. (2008). Aromaticity in spin-

polarized systems: Can rings be simultaneously alpha aromatic and beta antiaromatic? J.

Chem. Phys. 129, 164114.

[13] SHELXT program: G. M. Sheldrick, (2015). SHELXT – Integrated space-group and

crystal-structure determination. Acta Crystallogr., Sect. A: Found. Adv. A71, 3–8.

[14] Sheldrick, G. M. (2015). Crystal structure refinement with SHELXL. Acta

Crystallogr., Sect. C: Struct. Chem. C71, 3–8.

[15] Spek, A. L. (2015). PLATON SQUEEZE: a tool for the calculation of the disordered

solvent contribution to the calculated structure factors. Acta Crystallogr., Sect. C: Struct.

Chem. C71, 9–18.

http://reference.iucr.org/dictionary/Refinement

S51

6. Appendix: Cartesian coordinates of the optimized geometry

8MC (C2v)-singlet:

C 1.21051400 -5.96070100 -0.27010400

C 1.18945100 -4.73657900 0.52614900

C 0.00000000 -4.16538400 0.95788500

C -1.18945100 -4.73657900 0.52614900

C -1.21051400 -5.96070100 -0.27010400

C 0.00000000 -6.59001200 -0.62293800

C -2.55273200 -6.16744900 -0.68738200

C 2.55273200 -6.16744900 -0.68738200

C 2.50821400 -4.19185700 0.53144500

C -2.50821400 -4.19185700 0.53144500

C 3.35594100 -5.06653200 -0.26082400

C 4.65392500 -4.65392500 -0.61725100

C 5.06652900 -3.35594200 -0.26082800

C 4.19185700 -2.50821300 0.53144000

C 2.94188800 -2.94188900 0.95296700

C -2.94188800 -2.94188900 0.95296700

C -4.19185700 -2.50821300 0.53144000

C -5.06652900 -3.35594200 -0.26082800

C -4.65392500 -4.65392500 -0.61725100

C -3.35594100 -5.06653200 -0.26082400

C 5.96069800 1.21051500 -0.27011700

C 4.73657500 1.18945100 0.52614000

C 4.16538200 0.00000000 0.95787700

C 4.73657500 -1.18945100 0.52614000

C 5.96069800 -1.21051500 -0.27011700

C 6.59000900 0.00000000 -0.62295100

C 6.16744400 -2.55273000 -0.68739500

C 6.16744400 2.55273000 -0.68739500

C -1.21051400 5.96070100 -0.27010400

C -1.18945100 4.73657900 0.52614900

C 0.00000000 4.16538400 0.95788500

C 1.18945100 4.73657900 0.52614900

C 1.21051400 5.96070100 -0.27010400

C 0.00000000 6.59001200 -0.62293800

C 2.55273200 6.16744900 -0.68738200

C -2.55273200 6.16744900 -0.68738200

C -2.50821400 4.19185700 0.53144500

C 2.50821400 4.19185700 0.53144500

C -3.35594100 5.06653200 -0.26082400

C -4.65392500 4.65392500 -0.61725100

C -5.06652900 3.35594200 -0.26082800

C -4.19185700 2.50821300 0.53144000

S52

C -2.94188800 2.94188900 0.95296700

C 2.94188800 2.94188900 0.95296700

C 4.19185700 2.50821300 0.53144000

C 5.06652900 3.35594200 -0.26082800

C 4.65392500 4.65392500 -0.61725100

C 3.35594100 5.06653200 -0.26082400

C -5.96069800 -1.21051500 -0.27011700

C -4.73657500 -1.18945100 0.52614000

C -4.16538200 0.00000000 0.95787700

C -4.73657500 1.18945100 0.52614000

C -5.96069800 1.21051500 -0.27011700

C -6.59000900 0.00000000 -0.62295100

C -6.16744400 2.55273000 -0.68739500

C -6.16744400 -2.55273000 -0.68739500

H 0.00000000 -3.23300800 1.51593600

H 0.00000000 -7.48113700 -1.24527500

H 5.28247900 -5.28248100 -1.24310800

H 2.27957300 -2.27957200 1.50426800

H -2.27957300 -2.27957200 1.50426800

H -5.28247900 -5.28248100 -1.24310800

H 3.23300900 0.00000000 1.51593300

H 7.48113200 0.00000000 -1.24529000

H 0.00000000 3.23300800 1.51593600

H 0.00000000 7.48113700 -1.24527500

H -5.28247900 5.28248100 -1.24310800

H -2.27957300 2.27957200 1.50426800

H 2.27957300 2.27957200 1.50426800

H 5.28247900 5.28248100 -1.24310800

H -3.23300900 0.00000000 1.51593300

H -7.48113200 0.00000000 -1.24529000

H 2.89473900 6.98368900 -1.31343400

H -6.98368100 2.89474000 -1.31345000

H -6.98368100 -2.89474000 -1.31345000

H -2.89473900 -6.98368900 -1.31343400

H 6.98368100 -2.89474000 -1.31345000

H 6.98368100 2.89474000 -1.31345000

H -2.89473900 6.98368900 -1.31343400

H 2.89473900 -6.98368900 -1.31343400

8MC (C2v)-triplet:

C 1.20974500 -5.94876800 -0.27858100

C 1.19058500 -4.73543800 0.54044100

C 0.00000000 -4.17460800 0.98453500

C -1.19058500 -4.73543800 0.54044100

C -1.20974500 -5.94876800 -0.27858100

S53

C 0.00000000 -6.57201600 -0.64230200

C -2.54831700 -6.15193600 -0.70716200

C 2.54831700 -6.15193600 -0.70716200

C 2.50826400 -4.19450400 0.54826500

C -2.50826400 -4.19450400 0.54826500

C 3.35052100 -5.06144000 -0.26550800

C 4.64416200 -4.64415800 -0.63268500

C 5.06144200 -3.35052000 -0.26550400

C 4.19450800 -2.50826200 0.54826700

C 2.94786300 -2.94786300 0.97495800

C -2.94786300 -2.94786300 0.97495800

C -4.19450800 -2.50826200 0.54826700

C -5.06144200 -3.35052000 -0.26550400

C -4.64416200 -4.64415800 -0.63268500

C -3.35052100 -5.06144000 -0.26550800

C 5.94877300 1.20974500 -0.27858100

C 4.73543800 1.19058500 0.54044300

C 4.17461000 0.00000000 0.98453700

C 4.73543800 -1.19058500 0.54044300

C 5.94877300 -1.20974500 -0.27858100

C 6.57202000 0.00000000 -0.64230000

C 6.15194200 -2.54831400 -0.70715800

C 6.15194200 2.54831400 -0.70715800

C -1.20974500 5.94876800 -0.27858100

C -1.19058500 4.73543800 0.54044100

C 0.00000000 4.17460800 0.98453500

C 1.19058500 4.73543800 0.54044100

C 1.20974500 5.94876800 -0.27858100

C 0.00000000 6.57201600 -0.64230200

C 2.54831700 6.15193600 -0.70716200

C -2.54831700 6.15193600 -0.70716200

C -2.50826400 4.19450400 0.54826500

C 2.50826400 4.19450400 0.54826500

C -3.35052100 5.06144000 -0.26550800

C -4.64416200 4.64415800 -0.63268500

C -5.06144200 3.35052000 -0.26550400

C -4.19450800 2.50826200 0.54826700

C -2.94786300 2.94786300 0.97495800

C 2.94786300 2.94786300 0.97495800

C 4.19450800 2.50826200 0.54826700

C 5.06144200 3.35052000 -0.26550400

C 4.64416200 4.64415800 -0.63268500

C 3.35052100 5.06144000 -0.26550800

C -5.94877300 -1.20974500 -0.27858100

C -4.73543800 -1.19058500 0.54044300

C -4.17461000 0.00000000 0.98453700

S54

C -4.73543800 1.19058500 0.54044300

C -5.94877300 1.20974500 -0.27858100

C -6.57202000 0.00000000 -0.64230000

C -6.15194200 2.54831400 -0.70715800

C -6.15194200 -2.54831400 -0.70715800

H 0.00000000 -3.25157200 1.55776800

H 0.00000000 -7.45306000 -1.27908800

H 5.26524200 -5.26523700 -1.27375600

H 2.28980600 -2.28980600 1.53660700

H -2.28980600 -2.28980600 1.53660700

H -5.26524200 -5.26523700 -1.27375600

H 3.25157400 0.00000000 1.55777100

H 7.45306600 0.00000000 -1.27908400

H 0.00000000 3.25157200 1.55776800

H 0.00000000 7.45306000 -1.27908800

H -5.26524200 5.26523700 -1.27375600

H -2.28980600 2.28980600 1.53660700

H 2.28980600 2.28980600 1.53660700

H 5.26524200 5.26523700 -1.27375600

H -3.25157400 0.00000000 1.55777100

H -7.45306600 0.00000000 -1.27908400

H 2.88526500 6.95788300 -1.34905700

H -6.95788800 2.88526600 -1.34905200

H -6.95788800 -2.88526600 -1.34905200

H -2.88526500 -6.95788300 -1.34905700

H 6.95788800 -2.88526600 -1.34905200

H 6.95788800 2.88526600 -1.34905200

H -2.88526500 6.95788300 -1.34905700

H 2.88526500 -6.95788300 -1.34905700

8MC (C2v)-quintet:

C 1.20847900 -5.93642700 -0.28120600

C 1.18920200 -4.73379200 0.52933500

C 0.00000000 -4.16780600 0.96954000

C -1.18920200 -4.73379200 0.52933500

C -1.20847900 -5.93642700 -0.28120600

C 0.00000000 -6.55998000 -0.64725600

C -2.55811000 -6.14386100 -0.71056300

C 2.55811000 -6.14386100 -0.71056300

C 2.52020300 -4.18332800 0.53524000

C -2.52020300 -4.18332800 0.53524000

C 3.36250200 -5.05259300 -0.27411200

C 4.66135400 -4.64316500 -0.63151700

C 5.08119600 -3.34823400 -0.26430800

C 4.21053600 -2.50417300 0.54154700

S55

C 2.95447300 -2.94922800 0.97086100

C -2.95447300 -2.94922800 0.97086100

C -4.21053600 -2.50417300 0.54154700

C -5.08119600 -3.34823400 -0.26430800

C -4.66135400 -4.64316500 -0.63151700

C -3.36250200 -5.05259300 -0.27411200

C 5.97485200 1.21204400 -0.25661900

C 4.75526500 1.19343500 0.54838400

C 4.18248600 0.00000000 0.97267900

C 4.75526500 -1.19343500 0.54838400

C 5.97485200 -1.21204400 -0.25661900

C 6.59904400 0.00000000 -0.61532300

C 6.18332600 -2.54804400 -0.69083500

C 6.18332600 2.54804400 -0.69083500

C -1.20847900 5.93642700 -0.28120600

C -1.18920200 4.73379200 0.52933500

C 0.00000000 4.16780600 0.96954000

C 1.18920200 4.73379200 0.52933500

C 1.20847900 5.93642700 -0.28120600

C 0.00000000 6.55998000 -0.64725600

C 2.55811000 6.14386100 -0.71056300

C -2.55811000 6.14386100 -0.71056300

C -2.52020300 4.18332800 0.53524000

C 2.52020300 4.18332800 0.53524000

C -3.36250200 5.05259300 -0.27411200

C -4.66135400 4.64316500 -0.63151700

C -5.08119600 3.34823400 -0.26430800

C -4.21053600 2.50417300 0.54154700

C -2.95447300 2.94922800 0.97086100

C 2.95447300 2.94922800 0.97086100

C 4.21053600 2.50417300 0.54154700

C 5.08119600 3.34823400 -0.26430800

C 4.66135400 4.64316500 -0.63151700

C 3.36250200 5.05259300 -0.27411200

C -5.97485200 -1.21204400 -0.25661900

C -4.75526500 -1.19343500 0.54838400

C -4.18248600 0.00000000 0.97267900

C -4.75526500 1.19343500 0.54838400

C -5.97485200 1.21204400 -0.25661900

C -6.59904400 0.00000000 -0.61532300

C -6.18332600 2.54804400 -0.69083500

C -6.18332600 -2.54804400 -0.69083500

H 0.00000000 -3.24186600 1.53772500

H 0.00000000 -7.44095100 -1.28390200

H 5.28485000 -5.26917900 -1.26496700

H 2.29755200 -2.29167800 1.53383100

S56

H -2.29755200 -2.29167800 1.53383100

H -5.28485000 -5.26917900 -1.26496700

H 3.24951400 0.00000000 1.53050900

H 7.48486300 0.00000000 -1.24596900

H 0.00000000 3.24186600 1.53772500

H 0.00000000 7.44095100 -1.28390200

H -5.28485000 5.26917900 -1.26496700

H -2.29755200 2.29167800 1.53383100

H 2.29755200 2.29167800 1.53383100

H 5.28485000 5.26917900 -1.26496700

H -3.24951400 0.00000000 1.53050900

H -7.48486300 0.00000000 -1.24596900

H 2.89290200 6.95367400 -1.34876500

H -6.99469100 2.88478800 -1.32543800

H -6.99469100 -2.88478800 -1.32543800

H -2.89290200 -6.95367400 -1.34876500

H 6.99469100 -2.88478800 -1.32543800

H 6.99469100 2.88478800 -1.32543800

H -2.89290200 6.95367400 -1.34876500

H 2.89290200 -6.95367400 -1.34876500

8MC (C2v)-septet:

C 1.21017000 -5.95469000 -0.24460300

C 1.18961400 -4.73909300 0.52892000

C 0.00000000 -4.15413900 0.94384900

C -1.18961400 -4.73909300 0.52892000

C -1.21017000 -5.95469000 -0.24460300

C 0.00000000 -6.58357300 -0.59944100

C -2.56663500 -6.16922300 -0.66875700

C 2.56663500 -6.16922300 -0.66875700

C 2.52448500 -4.18778000 0.52288800

C -2.52448500 -4.18778000 0.52288800

C 3.36800200 -5.06937900 -0.25378600

C 4.68129900 -4.66281900 -0.60660800

C 5.09331400 -3.36768700 -0.26211800

C 4.21584200 -2.51504300 0.50955000

C 2.95932600 -2.93782500 0.93411000

C -2.95932600 -2.93782500 0.93411000

C -4.21584200 -2.51504300 0.50955000

C -5.09331400 -3.36768700 -0.26211800

C -4.68129900 -4.66281900 -0.60660800

C -3.36800200 -5.06937900 -0.25378600

C 5.99467300 1.21316000 -0.27130500

C 4.76689100 1.18920500 0.50356800

C 4.18603200 0.00000000 0.92446900

S57

C 4.76689100 -1.18920500 0.50356800

C 5.99467300 -1.21316000 -0.27130500

C 6.63153700 0.00000000 -0.61333700

C 6.21501500 -2.56287500 -0.67743900

C 6.21501500 2.56287500 -0.67743900

C -1.21017000 5.95469000 -0.24460300

C -1.18961400 4.73909300 0.52892000

C 0.00000000 4.15413900 0.94384900

C 1.18961400 4.73909300 0.52892000

C 1.21017000 5.95469000 -0.24460300

C 0.00000000 6.58357300 -0.59944100

C 2.56663500 6.16922300 -0.66875700

C -2.56663500 6.16922300 -0.66875700

C -2.52448500 4.18778000 0.52288800

C 2.52448500 4.18778000 0.52288800

C -3.36800200 5.06937900 -0.25378600

C -4.68129900 4.66281900 -0.60660800

C -5.09331400 3.36768700 -0.26211800

C -4.21584200 2.51504300 0.50955000

C -2.95932600 2.93782500 0.93411000

C 2.95932600 2.93782500 0.93411000

C 4.21584200 2.51504300 0.50955000

C 5.09331400 3.36768700 -0.26211800

C 4.68129900 4.66281900 -0.60660800

C 3.36800200 5.06937900 -0.25378600

C -5.99467300 -1.21316000 -0.27130500

C -4.76689100 -1.18920500 0.50356800

C -4.18603200 0.00000000 0.92446900

C -4.76689100 1.18920500 0.50356800

C -5.99467300 1.21316000 -0.27130500

C -6.63153700 0.00000000 -0.61333700

C -6.21501500 2.56287500 -0.67743900

C -6.21501500 -2.56287500 -0.67743900

H 0.00000000 -3.21209700 1.48578600

H 0.00000000 -7.47906400 -1.21599600

H 5.31127900 -5.30414200 -1.21756500

H 2.29977800 -2.26659400 1.47744900

H -2.29977800 -2.26659400 1.47744900

H -5.31127900 -5.30414200 -1.21756500

H 3.24615700 0.00000000 1.46948400

H 7.53368100 0.00000000 -1.21908200

H 0.00000000 3.21209700 1.48578600

H 0.00000000 7.47906400 -1.21599600

H -5.31127900 5.30414200 -1.21756500

H -2.29977800 2.26659400 1.47744900

H 2.29977800 2.26659400 1.47744900

S58

H 5.31127900 5.30414200 -1.21756500

H -3.24615700 0.00000000 1.46948400

H -7.53368100 0.00000000 -1.21908200

H 2.90475100 6.99434800 -1.28540800

H -7.04078000 2.90875800 -1.28770400

H -7.04078000 -2.90875800 -1.28770400

H -2.90475100 -6.99434800 -1.28540800

H 7.04078000 -2.90875800 -1.28770400

H 7.04078000 2.90875800 -1.28770400

H -2.90475100 6.99434800 -1.28540800

H 2.90475100 -6.99434800 -1.28540800

8MC (C2v)-nonet:

C 1.21146500 -5.99617200 -0.24816400

C 1.18674000 -4.77006800 0.49635300

C 0.00000000 -4.17579800 0.90299200

C -1.18674000 -4.77006800 0.49635300

C -1.21146500 -5.99617200 -0.24816400

C 0.00000000 -6.63713100 -0.58560300

C -2.57748100 -6.22259100 -0.64873500

C 2.57748100 -6.22259100 -0.64873500

C 2.53378500 -4.21208800 0.49634800

C -2.53378500 -4.21208800 0.49634800

C 3.38329700 -5.09656000 -0.24814300

C 4.69316500 -4.69316200 -0.58558200

C 5.09656300 -3.38329600 -0.24813900

C 4.21209000 -2.53378500 0.49635200

C 2.95268300 -2.95268200 0.90292000

C -2.95268300 -2.95268200 0.90292000

C -4.21209000 -2.53378500 0.49635200

C -5.09656300 -3.38329600 -0.24813900

C -4.69316500 -4.69316200 -0.58558200

C -3.38329700 -5.09656000 -0.24814300

C 5.99617600 1.21146500 -0.24815300

C 4.77007000 1.18674000 0.49636000

C 4.17579900 0.00000000 0.90299700

C 4.77007000 -1.18674000 0.49636000

C 5.99617600 -1.21146500 -0.24815300

C 6.63713600 0.00000000 -0.58559000

C 6.22259700 -2.57748100 -0.64872400

C 6.22259700 2.57748100 -0.64872400

C -1.21146500 5.99617200 -0.24816400

C -1.18674000 4.77006800 0.49635300

C 0.00000000 4.17579800 0.90299200

C 1.18674000 4.77006800 0.49635300

S59

C 1.21146500 5.99617200 -0.24816400

C 0.00000000 6.63713100 -0.58560300

C 2.57748100 6.22259100 -0.64873500

C -2.57748100 6.22259100 -0.64873500

C -2.53378500 4.21208800 0.49634800

C 2.53378500 4.21208800 0.49634800

C -3.38329700 5.09656000 -0.24814300

C -4.69316500 4.69316200 -0.58558200

C -5.09656300 3.38329600 -0.24813900

C -4.21209000 2.53378500 0.49635200

C -2.95268300 2.95268200 0.90292000

C 2.95268300 2.95268200 0.90292000

C 4.21209000 2.53378500 0.49635200

C 5.09656300 3.38329600 -0.24813900

C 4.69316500 4.69316200 -0.58558200

C 3.38329700 5.09656000 -0.24814300

C -5.99617600 -1.21146500 -0.24815300

C -4.77007000 -1.18674000 0.49636000

C -4.17579900 0.00000000 0.90299700

C -4.77007000 1.18674000 0.49636000

C -5.99617600 1.21146500 -0.24815300

C -6.63713600 0.00000000 -0.58559000

C -6.22259700 2.57748100 -0.64872400

C -6.22259700 -2.57748100 -0.64872400

H 0.00000000 -3.22489200 1.42852200

H 0.00000000 -7.54855400 -1.17736700

H 5.33764900 -5.33764600 -1.17732100

H 2.28020600 -2.28020700 1.42824300

H -2.28020600 -2.28020700 1.42824300

H -5.33764900 -5.33764600 -1.17732100

H 3.22489100 0.00000000 1.42852400

H 7.54856200 0.00000000 -1.17735100

H 0.00000000 3.22489200 1.42852200

H 0.00000000 7.54855400 -1.17736700

H -5.33764900 5.33764600 -1.17732100

H -2.28020600 2.28020700 1.42824300

H 2.28020600 2.28020700 1.42824300

H 5.33764900 5.33764600 -1.17732100

H -3.22489100 0.00000000 1.42852400

H -7.54856200 0.00000000 -1.17735100

H 2.92475700 7.06098100 -1.24132800

H -7.06098900 2.92475700 -1.24131400

H -7.06098900 -2.92475700 -1.24131400

H -2.92475700 -7.06098100 -1.24132800

H 7.06098900 -2.92475700 -1.24131400

H 7.06098900 2.92475700 -1.24131400

S60

H -2.92475700 7.06098100 -1.24132800

H 2.92475700 -7.06098100 -1.24132800

10MC (D2h)-singlet:

H 0.00000000 -8.80855700 2.85942500

H 0.00000000 -8.80855700 -2.85942500

H 0.00000000 -5.44234000 -7.48372300

H 0.00000000 0.00000000 -9.24885500

H 0.00000000 5.44234000 -7.48372300

H 0.00000000 8.80855700 -2.85942500

C 0.00000000 8.28328400 0.00000000

C 0.00000000 6.70137100 4.86128800

C 0.00000000 2.55988200 7.86651300

C 0.00000000 -2.55988200 7.86651300

C 0.00000000 -6.70137100 4.86128800

C 0.00000000 -8.28328400 0.00000000

C 0.00000000 -6.70137100 -4.86128800

C 0.00000000 -2.55988200 -7.86651300

C 0.00000000 2.55988200 -7.86651300

C 0.00000000 6.70137100 -4.86128800

H 0.00000000 9.36718800 0.00000000

H 0.00000000 7.57757100 5.49936600

H 0.00000000 2.89417800 8.89758800

H 0.00000000 -2.89417800 8.89758800

H 0.00000000 -7.57757100 5.49936600

H 0.00000000 -9.36718800 0.00000000

H 0.00000000 -7.57757100 -5.49936600

H 0.00000000 -2.89417800 -8.89758800

H 0.00000000 2.89417800 -8.89758800

H 0.00000000 7.57757100 -5.49936600

C 0.00000000 5.32927800 2.98566900

C 0.00000000 2.55476100 5.54305900

C 0.00000000 -1.19440500 5.98432300

C 0.00000000 -4.48887400 4.14043900

C 0.00000000 -6.06917600 0.71334200

C 0.00000000 -5.32927800 -2.98566900

C 0.00000000 -2.55476100 -5.54305900

C 0.00000000 1.19440500 -5.98432300

C 0.00000000 4.48887400 -4.14043900

C 0.00000000 6.06917600 -0.71334200

C 0.00000000 6.06917600 0.71334200

C 0.00000000 4.48887400 4.14043900

C 0.00000000 1.19440500 5.98432300

C 0.00000000 -2.55476100 5.54305900

C 0.00000000 -5.32927800 2.98566900

S61

C 0.00000000 -6.06917600 -0.71334200

C 0.00000000 -4.48887400 -4.14043900

C 0.00000000 -1.19440500 -5.98432300

C 0.00000000 2.55476100 -5.54305900

C 0.00000000 5.32927800 -2.98566900

C 0.00000000 6.71857100 3.44813000

C 0.00000000 3.40505000 6.73076500

C 0.00000000 -1.20463000 7.44312700

C 0.00000000 -5.35606500 5.31627300

C 0.00000000 -7.46517200 1.15589100

C 0.00000000 -6.71857100 -3.44813000

C 0.00000000 -3.40505000 -6.73076500

C 0.00000000 1.20463000 -7.44312700

C 0.00000000 5.35606500 -5.31627300

C 0.00000000 7.46517200 -1.15589100

C 0.00000000 7.46517200 1.15589100

C 0.00000000 5.35606500 5.31627300

C 0.00000000 1.20463000 7.44312700

C 0.00000000 -3.40505000 6.73076500

C 0.00000000 -6.71857100 3.44813000

C 0.00000000 -7.46517200 -1.15589100

C 0.00000000 -5.35606500 -5.31627300

C 0.00000000 -1.20463000 -7.44312700

C 0.00000000 3.40505000 -6.73076500

C 0.00000000 6.71857100 -3.44813000

10MC (D2h)-triplet:

H 0.00000000 3.98078800 1.29344600

H 0.00000000 2.46037500 3.38604000

H 0.00000000 0.00000000 4.18537300

H 0.00000000 -2.46037500 3.38604000

H 0.00000000 -3.98078800 1.29344600

H 0.00000000 -3.98078800 -1.29344600

H 0.00000000 -2.46037500 -3.38604000

H 0.00000000 0.00000000 -4.18537300

H 0.00000000 2.46037500 -3.38604000

H 0.00000000 3.98078800 -1.29344600

C 0.00000000 5.01462400 1.62932200

C 0.00000000 3.09924900 4.26550300

C 0.00000000 0.00000000 5.27240100

C 0.00000000 -3.09924900 4.26550300

C 0.00000000 -5.01462400 1.62932200

C 0.00000000 -5.01462400 -1.62932200

C 0.00000000 -3.09924900 -4.26550300

C 0.00000000 0.00000000 -5.27240100

S62

C 0.00000000 3.09924900 -4.26550300

C 0.00000000 5.01462400 -1.62932200

C 0.00000000 7.76814500 2.52400000

C 0.00000000 4.80091300 6.60787200

C 0.00000000 0.00000000 8.16764700

C 0.00000000 -4.80091300 6.60787200

C 0.00000000 -7.76814500 2.52400000

C 0.00000000 -7.76814500 -2.52400000

C 0.00000000 -4.80091300 -6.60787200

C 0.00000000 0.00000000 -8.16764700

C 0.00000000 4.80091300 -6.60787200

C 0.00000000 7.76814500 -2.52400000

H 0.00000000 8.80180800 2.85983400

H 0.00000000 5.43969500 7.48718600

H 0.00000000 0.00000000 9.25449500

H 0.00000000 -5.43969500 7.48718600

H 0.00000000 -8.80180800 2.85983400

H 0.00000000 -8.80180800 -2.85983400

H 0.00000000 -5.43969500 -7.48718600

H 0.00000000 0.00000000 -9.25449500

H 0.00000000 5.43969500 -7.48718600

H 0.00000000 8.80180800 -2.85983400

C 0.00000000 8.27614600 0.00000000

C 0.00000000 6.69555500 4.86457800

C 0.00000000 2.55741200 7.87087600

C 0.00000000 -2.55741200 7.87087600

C 0.00000000 -6.69555500 4.86457800

C 0.00000000 -8.27614600 0.00000000

C 0.00000000 -6.69555500 -4.86457800

C 0.00000000 -2.55741200 -7.87087600

C 0.00000000 2.55741200 -7.87087600

C 0.00000000 6.69555500 -4.86457800

H 0.00000000 9.36006700 0.00000000

H 0.00000000 7.57244700 5.50171300

H 0.00000000 2.89232800 8.90175500

H 0.00000000 -2.89232800 8.90175500

H 0.00000000 -7.57244700 5.50171300

H 0.00000000 -9.36006700 0.00000000

H 0.00000000 -7.57244700 -5.50171300

H 0.00000000 -2.89232800 -8.90175500

H 0.00000000 2.89232800 -8.90175500

H 0.00000000 7.57244700 -5.50171300

C 0.00000000 5.32498300 2.98622400

C 0.00000000 2.55266000 5.54564300

C 0.00000000 -1.19460500 5.98685400

C 0.00000000 -4.48563900 4.14141700

S63

C 0.00000000 -6.06323900 0.71396500

C 0.00000000 -5.32498300 -2.98622400

C 0.00000000 -2.55266000 -5.54564300

C 0.00000000 1.19460500 -5.98685400

C 0.00000000 4.48563900 -4.14141700

C 0.00000000 6.06323900 -0.71396500

C 0.00000000 6.06323900 0.71396500

C 0.00000000 4.48563900 4.14141700

C 0.00000000 1.19460500 5.98685400

C 0.00000000 -2.55266000 5.54564300

C 0.00000000 -5.32498300 2.98622400

C 0.00000000 -6.06323900 -0.71396500

C 0.00000000 -4.48563900 -4.14141700

C 0.00000000 -1.19460500 -5.98685400

C 0.00000000 2.55266000 -5.54564300

C 0.00000000 5.32498300 -2.98622400

C 0.00000000 6.71240100 3.44802900

C 0.00000000 3.40366300 6.73478100

C 0.00000000 -1.20503100 7.44909800

C 0.00000000 -5.35352900 5.31827600

C 0.00000000 -7.45712000 1.15589300

C 0.00000000 -6.71240100 -3.44802900

C 0.00000000 -3.40366300 -6.73478100

C 0.00000000 1.20503100 -7.44909800

C 0.00000000 5.35352900 -5.31827600

C 0.00000000 7.45712000 -1.15589300

C 0.00000000 7.45712000 1.15589300

C 0.00000000 5.35352900 5.31827600

C 0.00000000 1.20503100 7.44909800

C 0.00000000 -3.40366300 6.73478100

C 0.00000000 -6.71240100 3.44802900

C 0.00000000 -7.45712000 -1.15589300

C 0.00000000 -5.35352900 -5.31827600

C 0.00000000 -1.20503100 -7.44909800

C 0.00000000 3.40366300 -6.73478100

C 0.00000000 6.71240100 -3.44802900

10MC (D2h)-quintet:

H 0.00000000 3.94876200 1.31003100

H 0.00000000 2.43801500 3.42659900

H 0.00000000 0.00000000 4.23296700

H 0.00000000 -2.43801500 3.42659900

H 0.00000000 -3.94876200 1.31003100

H 0.00000000 -3.94876200 -1.31003100

H 0.00000000 -2.43801500 -3.42659900

S64

H 0.00000000 0.00000000 -4.23296700

H 0.00000000 2.43801500 -3.42659900

H 0.00000000 3.94876200 -1.31003100

C 0.00000000 4.98483600 1.63946700

C 0.00000000 3.08592500 4.29945800

C 0.00000000 0.00000000 5.31994100

C 0.00000000 -3.08592500 4.29945800

C 0.00000000 -4.98483600 1.63946700

C 0.00000000 -4.98483600 -1.63946700

C 0.00000000 -3.08592500 -4.29945800

C 0.00000000 0.00000000 -5.31994100

C 0.00000000 3.08592500 -4.29945800

C 0.00000000 4.98483600 -1.63946700

C 0.00000000 7.73185600 2.52803100

C 0.00000000 4.79217800 6.63787600

C 0.00000000 0.00000000 8.21915600

C 0.00000000 -4.79217800 6.63787600

C 0.00000000 -7.73185600 2.52803100

C 0.00000000 -7.73185600 -2.52803100

C 0.00000000 -4.79217800 -6.63787600

C 0.00000000 0.00000000 -8.21915600

C 0.00000000 4.79217800 -6.63787600

C 0.00000000 7.73185600 -2.52803100

H 0.00000000 8.76787500 2.85801000

H 0.00000000 5.43934900 7.51108400

H 0.00000000 0.00000000 9.30577000

H 0.00000000 -5.43934900 7.51108400

H 0.00000000 -8.76787500 2.85801000

H 0.00000000 -8.76787500 -2.85801000

H 0.00000000 -5.43934900 -7.51108400

H 0.00000000 0.00000000 -9.30577000

H 0.00000000 5.43934900 -7.51108400

H 0.00000000 8.76787500 -2.85801000

C 0.00000000 8.23477700 0.00000000

C 0.00000000 6.67380500 4.88146400

C 0.00000000 2.55622800 7.92041400

C 0.00000000 -2.55622800 7.92041400

C 0.00000000 -6.67380500 4.88146400

C 0.00000000 -8.23477700 0.00000000

C 0.00000000 -6.67380500 -4.88146400

C 0.00000000 -2.55622800 -7.92041400

C 0.00000000 2.55622800 -7.92041400

C 0.00000000 6.67380500 -4.88146400

H 0.00000000 9.31916200 0.00000000

H 0.00000000 7.55504600 5.51281200

H 0.00000000 2.89535200 8.94949700

S65

H 0.00000000 -2.89535200 8.94949700

H 0.00000000 -7.55504600 5.51281200

H 0.00000000 -9.31916200 0.00000000

H 0.00000000 -7.55504600 -5.51281200

H 0.00000000 -2.89535200 -8.94949700

H 0.00000000 2.89535200 -8.94949700

H 0.00000000 7.55504600 -5.51281200

C 0.00000000 5.30255700 2.99648000

C 0.00000000 2.54959900 5.58584100

C 0.00000000 -1.19485800 6.03333500

C 0.00000000 -4.46921300 4.16204100

C 0.00000000 -6.02743100 0.71861100

C 0.00000000 -5.30255700 -2.99648000

C 0.00000000 -2.54959900 -5.58584100

C 0.00000000 1.19485800 -6.03333500

C 0.00000000 4.46921300 -4.16204100

C 0.00000000 6.02743100 -0.71861100

C 0.00000000 6.02743100 0.71861100

C 0.00000000 4.46921300 4.16204100

C 0.00000000 1.19485800 6.03333500

C 0.00000000 -2.54959900 5.58584100

C 0.00000000 -5.30255700 2.99648000

C 0.00000000 -6.02743100 -0.71861100

C 0.00000000 -4.46921300 -4.16204100

C 0.00000000 -1.19485800 -6.03333500

C 0.00000000 2.54959900 -5.58584100

C 0.00000000 5.30255700 -2.99648000

C 0.00000000 6.68339700 3.44930900

C 0.00000000 3.40559800 6.77055500

C 0.00000000 -1.20804400 7.49950800

C 0.00000000 -5.34333100 5.33272900

C 0.00000000 -7.41335700 1.15467000

C 0.00000000 -6.68339700 -3.44930900

C 0.00000000 -3.40559800 -6.77055500

C 0.00000000 1.20804400 -7.49950800

C 0.00000000 5.34333100 -5.33272900

C 0.00000000 7.41335700 -1.15467000

C 0.00000000 7.41335700 1.15467000

C 0.00000000 5.34333100 5.33272900

C 0.00000000 1.20804400 7.49950800

C 0.00000000 -3.40559800 6.77055500

C 0.00000000 -6.68339700 3.44930900

C 0.00000000 -7.41335700 -1.15467000

C 0.00000000 -5.34333100 -5.33272900

C 0.00000000 -1.20804400 -7.49950800

C 0.00000000 3.40559800 -6.77055500

S66

C 0.00000000 6.68339700 -3.44930900

10MC (D2h)-septet:

H 0.00000000 4.00689300 1.30067100

H 0.00000000 2.47485700 3.40246000

H 0.00000000 0.00000000 4.20440800

H 0.00000000 -2.47485700 3.40246000

H 0.00000000 -4.00689300 1.30067100

H 0.00000000 -4.00689300 -1.30067100

H 0.00000000 -2.47485700 -3.40246000

H 0.00000000 0.00000000 -4.20440800

H 0.00000000 2.47485700 -3.40246000

H 0.00000000 4.00689300 -1.30067100

C 0.00000000 5.04100700 1.63684800

C 0.00000000 3.11369700 4.28191600

C 0.00000000 0.00000000 5.29121500

C 0.00000000 -3.11369700 4.28191600

C 0.00000000 -5.04100700 1.63684800

C 0.00000000 -5.04100700 -1.63684800

C 0.00000000 -3.11369700 -4.28191600

C 0.00000000 0.00000000 -5.29121500

C 0.00000000 3.11369700 -4.28191600

C 0.00000000 5.04100700 -1.63684800

C 0.00000000 7.79085400 2.52536700

C 0.00000000 4.81587700 6.61299100

C 0.00000000 0.00000000 8.17555000

C 0.00000000 -4.81587700 6.61299100

C 0.00000000 -7.79085400 2.52536700

C 0.00000000 -7.79085400 -2.52536700

C 0.00000000 -4.81587700 -6.61299100

C 0.00000000 0.00000000 -8.17555000

C 0.00000000 4.81587700 -6.61299100

C 0.00000000 7.79085400 -2.52536700

H 0.00000000 8.82438500 2.86207200

H 0.00000000 5.45403500 7.49262400

H 0.00000000 0.00000000 9.26214600

H 0.00000000 -5.45403500 7.49262400

H 0.00000000 -8.82438500 2.86207200

H 0.00000000 -8.82438500 -2.86207200

H 0.00000000 -5.45403500 -7.49262400

H 0.00000000 0.00000000 -9.26214600

H 0.00000000 5.45403500 -7.49262400

H 0.00000000 8.82438500 -2.86207200

C 0.00000000 8.30494100 0.00000000

C 0.00000000 6.72007000 4.86635200

S67

C 0.00000000 2.56818800 7.87871200

C 0.00000000 -2.56818800 7.87871200

C 0.00000000 -6.72007000 4.86635200

C 0.00000000 -8.30494100 0.00000000

C 0.00000000 -6.72007000 -4.86635200

C 0.00000000 -2.56818800 -7.87871200

C 0.00000000 2.56818800 -7.87871200

C 0.00000000 6.72007000 -4.86635200

H 0.00000000 9.38866400 0.00000000

H 0.00000000 7.59597000 5.50473000

H 0.00000000 2.90228800 8.90991900

H 0.00000000 -2.90228800 8.90991900

H 0.00000000 -7.59597000 5.50473000

H 0.00000000 -9.38866400 0.00000000

H 0.00000000 -7.59597000 -5.50473000

H 0.00000000 -2.90228800 -8.90991900

H 0.00000000 2.90228800 -8.90991900

H 0.00000000 7.59597000 -5.50473000

C 0.00000000 5.35177100 2.98942600

C 0.00000000 2.57501400 5.55822100

C 0.00000000 -1.19332000 6.00908100

C 0.00000000 -4.50865200 4.15517800

C 0.00000000 -6.09286900 0.71383700

C 0.00000000 -5.35177100 -2.98942600

C 0.00000000 -2.57501400 -5.55822100

C 0.00000000 1.19332000 -6.00908100

C 0.00000000 4.50865200 -4.15517800

C 0.00000000 6.09286900 -0.71383700

C 0.00000000 6.09286900 0.71383700

C 0.00000000 4.50865200 4.15517800

C 0.00000000 1.19332000 6.00908100

C 0.00000000 -2.57501400 5.55822100

C 0.00000000 -5.35177100 2.98942600

C 0.00000000 -6.09286900 -0.71383700

C 0.00000000 -4.50865200 -4.15517800

C 0.00000000 -1.19332000 -6.00908100

C 0.00000000 2.57501400 -5.55822100

C 0.00000000 5.35177100 -2.98942600

C 0.00000000 6.73401500 3.44989400

C 0.00000000 3.41808000 6.73752300

C 0.00000000 -1.20431500 7.45399200

C 0.00000000 -5.36860800 5.32121000

C 0.00000000 -7.48099700 1.15462700

C 0.00000000 -6.73401500 -3.44989400

C 0.00000000 -3.41808000 -6.73752300

C 0.00000000 1.20431500 -7.45399200

S68

C 0.00000000 5.36860800 -5.32121000

C 0.00000000 7.48099700 -1.15462700

C 0.00000000 7.48099700 1.15462700

C 0.00000000 5.36860800 5.32121000

C 0.00000000 1.20431500 7.45399200

C 0.00000000 -3.41808000 6.73752300

C 0.00000000 -6.73401500 3.44989400

C 0.00000000 -7.48099700 -1.15462700

C 0.00000000 -5.36860800 -5.32121000

C 0.00000000 -1.20431500 -7.45399200

C 0.00000000 3.41808000 -6.73752300

C 0.00000000 6.73401500 -3.44989400

10MC (D2h)-nonet:

H 0.00000000 4.02083500 1.29368800

H 0.00000000 2.47357600 3.41646900

H 0.00000000 0.00000000 4.22664200

H 0.00000000 -2.47357600 3.41646900

H 0.00000000 -4.02083500 1.29368800

H 0.00000000 -4.02083500 -1.29368800

H 0.00000000 -2.47357600 -3.41646900

H 0.00000000 0.00000000 -4.22664200

H 0.00000000 2.47357600 -3.41646900

H 0.00000000 4.02083500 -1.29368800

C 0.00000000 5.05248900 1.63608000

C 0.00000000 3.11591000 4.29357000

C 0.00000000 0.00000000 5.31354400

C 0.00000000 -3.11591000 4.29357000

C 0.00000000 -5.05248900 1.63608000

C 0.00000000 -5.05248900 -1.63608000

C 0.00000000 -3.11591000 -4.29357000

C 0.00000000 0.00000000 -5.31354400

C 0.00000000 3.11591000 -4.29357000

C 0.00000000 5.05248900 -1.63608000

C 0.00000000 7.79480400 2.53058700

C 0.00000000 4.81057600 6.62287900

C 0.00000000 0.00000000 8.20035500

C 0.00000000 -4.81057600 6.62287900

C 0.00000000 -7.79480400 2.53058700

C 0.00000000 -7.79480400 -2.53058700

C 0.00000000 -4.81057600 -6.62287900

C 0.00000000 0.00000000 -8.20035500

C 0.00000000 4.81057600 -6.62287900

C 0.00000000 7.79480400 -2.53058700

H 0.00000000 8.82586200 2.87365600

S69

H 0.00000000 5.45310300 7.49939000

H 0.00000000 0.00000000 9.28689000

H 0.00000000 -5.45310300 7.49939000

H 0.00000000 -8.82586200 2.87365600

H 0.00000000 -8.82586200 -2.87365600

H 0.00000000 -5.45310300 -7.49939000

H 0.00000000 0.00000000 -9.28689000

H 0.00000000 5.45310300 -7.49939000

H 0.00000000 8.82586200 -2.87365600

C 0.00000000 8.32162200 0.00000000

C 0.00000000 6.71033600 4.87300000

C 0.00000000 2.56544200 7.90425700

C 0.00000000 -2.56544200 7.90425700

C 0.00000000 -6.71033600 4.87300000

C 0.00000000 -8.32162200 0.00000000

C 0.00000000 -6.71033600 -4.87300000

C 0.00000000 -2.56544200 -7.90425700

C 0.00000000 2.56544200 -7.90425700

C 0.00000000 6.71033600 -4.87300000

H 0.00000000 9.40494900 0.00000000

H 0.00000000 7.58617000 5.51182900

H 0.00000000 2.90330500 8.93384100

H 0.00000000 -2.90330500 8.93384100

H 0.00000000 -7.58617000 5.51182900

H 0.00000000 -9.40494900 0.00000000

H 0.00000000 -7.58617000 -5.51182900

H 0.00000000 -2.90330500 -8.93384100

H 0.00000000 2.90330500 -8.93384100

H 0.00000000 7.58617000 -5.51182900

C 0.00000000 5.35859700 2.98969600

C 0.00000000 2.57271000 5.58060300

C 0.00000000 -1.19473800 6.03083800

C 0.00000000 -4.50022200 4.16842300

C 0.00000000 -6.11203800 0.72209500

C 0.00000000 -5.35859700 -2.98969600

C 0.00000000 -2.57271000 -5.58060300

C 0.00000000 1.19473800 -6.03083800

C 0.00000000 4.50022200 -4.16842300

C 0.00000000 6.11203800 -0.72209500

C 0.00000000 6.11203800 0.72209500

C 0.00000000 4.50022200 4.16842300

C 0.00000000 1.19473800 6.03083800

C 0.00000000 -2.57271000 5.58060300

C 0.00000000 -5.35859700 2.98969600

C 0.00000000 -6.11203800 -0.72209500

C 0.00000000 -4.50022200 -4.16842300

S70

C 0.00000000 -1.19473800 -6.03083800

C 0.00000000 2.57271000 -5.58060300

C 0.00000000 5.35859700 -2.98969600

C 0.00000000 6.72935300 3.45092300

C 0.00000000 3.41450900 6.75215000

C 0.00000000 -1.20614900 7.47956700

C 0.00000000 -5.35817400 5.32793000

C 0.00000000 -7.48990700 1.16272500

C 0.00000000 -6.72935300 -3.45092300

C 0.00000000 -3.41450900 -6.75215000

C 0.00000000 1.20614900 -7.47956700

C 0.00000000 5.35817400 -5.32793000

C 0.00000000 7.48990700 -1.16272500

C 0.00000000 7.48990700 1.16272500

C 0.00000000 5.35817400 5.32793000

C 0.00000000 1.20614900 7.47956700

C 0.00000000 -3.41450900 6.75215000

C 0.00000000 -6.72935300 3.45092300

C 0.00000000 -7.48990700 -1.16272500

C 0.00000000 -5.35817400 -5.32793000

C 0.00000000 -1.20614900 -7.47956700

C 0.00000000 3.41450900 -6.75215000

C 0.00000000 6.72935300 -3.45092300

10MC (D2h)-11-et:

H 0.00000000 4.00980900 1.30287200

H 0.00000000 2.47831500 3.41072300

H 0.00000000 0.00000000 4.21589900

H 0.00000000 -2.47831500 3.41072300

H 0.00000000 -4.00980900 1.30287200

H 0.00000000 -4.00980900 -1.30287200

H 0.00000000 -2.47831500 -3.41072300

H 0.00000000 0.00000000 -4.21589900

H 0.00000000 2.47831500 -3.41072300

H 0.00000000 4.00980900 -1.30287200

C 0.00000000 5.04353000 1.63871400

C 0.00000000 3.11711100 4.29009600

C 0.00000000 0.00000000 5.30280700

C 0.00000000 -3.11711100 4.29009600

C 0.00000000 -5.04353000 1.63871400

C 0.00000000 -5.04353000 -1.63871400

C 0.00000000 -3.11711100 -4.29009600

C 0.00000000 0.00000000 -5.30280700

C 0.00000000 3.11711100 -4.29009600

C 0.00000000 5.04353000 -1.63871400

S71

C 0.00000000 7.78956200 2.53095400

C 0.00000000 4.81415000 6.62607700

C 0.00000000 0.00000000 8.19015900

C 0.00000000 -4.81415000 6.62607700

C 0.00000000 -7.78956200 2.53095400

C 0.00000000 -7.78956200 -2.53095400

C 0.00000000 -4.81415000 -6.62607700

C 0.00000000 0.00000000 -8.19015900

C 0.00000000 4.81415000 -6.62607700

C 0.00000000 7.78956200 -2.53095400

H 0.00000000 8.82279600 2.86665100

H 0.00000000 5.45266300 7.50503200

H 0.00000000 0.00000000 9.27655800

H 0.00000000 -5.45266300 7.50503200

H 0.00000000 -8.82279600 2.86665100

H 0.00000000 -8.82279600 -2.86665100

H 0.00000000 -5.45266300 -7.50503200

H 0.00000000 0.00000000 -9.27655800

H 0.00000000 5.45266300 -7.50503200

H 0.00000000 8.82279600 -2.86665100

C 0.00000000 8.30619200 0.00000000

C 0.00000000 6.71986500 4.88222200

C 0.00000000 2.56670400 7.89944700

C 0.00000000 -2.56670400 7.89944700

C 0.00000000 -6.71986500 4.88222200

C 0.00000000 -8.30619200 0.00000000

C 0.00000000 -6.71986500 -4.88222200

C 0.00000000 -2.56670400 -7.89944700

C 0.00000000 2.56670400 -7.89944700

C 0.00000000 6.71986500 -4.88222200

H 0.00000000 9.38939300 0.00000000

H 0.00000000 7.59618000 5.51892700

H 0.00000000 2.90140800 8.92963900

H 0.00000000 -2.90140800 8.92963900

H 0.00000000 -7.59618000 5.51892700

H 0.00000000 -9.38939300 0.00000000

H 0.00000000 -7.59618000 -5.51892700

H 0.00000000 -2.90140800 -8.92963900

H 0.00000000 2.90140800 -8.92963900

H 0.00000000 7.59618000 -5.51892700

C 0.00000000 5.35595700 2.99588100

C 0.00000000 2.57204700 5.57166800

C 0.00000000 -1.19421900 6.01931400

C 0.00000000 -4.50440500 4.16789600

C 0.00000000 -6.09398600 0.72435300

C 0.00000000 -5.35595700 -2.99588100

S72

C 0.00000000 -2.57204700 -5.57166800

C 0.00000000 1.19421900 -6.01931400

C 0.00000000 4.50440500 -4.16789600

C 0.00000000 6.09398600 -0.72435300

C 0.00000000 6.09398600 0.72435300

C 0.00000000 4.50440500 4.16789600

C 0.00000000 1.19421900 6.01931400

C 0.00000000 -2.57204700 5.57166800

C 0.00000000 -5.35595700 2.99588100

C 0.00000000 -6.09398600 -0.72435300

C 0.00000000 -4.50440500 -4.16789600

C 0.00000000 -1.19421900 -6.01931400

C 0.00000000 2.57204700 -5.57166800

C 0.00000000 5.35595700 -2.99588100

C 0.00000000 6.73131400 3.45455700

C 0.00000000 3.41512600 6.75117700

C 0.00000000 -1.20540400 7.46910400

C 0.00000000 -5.36559200 5.33423400

C 0.00000000 -7.47626800 1.16171900

C 0.00000000 -6.73131400 -3.45455700

C 0.00000000 -3.41512600 -6.75117700

C 0.00000000 1.20540400 -7.46910400

C 0.00000000 5.36559200 -5.33423400

C 0.00000000 7.47626800 -1.16171900

C 0.00000000 7.47626800 1.16171900

C 0.00000000 5.36559200 5.33423400

C 0.00000000 1.20540400 7.46910400

C 0.00000000 -3.41512600 6.75117700

C 0.00000000 -6.73131400 3.45455700

C 0.00000000 -7.47626800 -1.16171900

C 0.00000000 -5.36559200 -5.33423400

C 0.00000000 -1.20540400 -7.46910400

C 0.00000000 3.41512600 -6.75117700

C 0.00000000 6.73131400 -3.45455700

8MC-M (singlet, for NMR calculation):

C -5.11809265 3.27771517 -1.21291696

C -4.23546840 2.44523259 -2.03376163

C -2.99578793 2.90227583 -2.46079285

C -2.57643653 4.15460312 -2.03108948

C -3.43653495 5.01013454 -1.20992576

C -4.72163030 4.57468450 -0.83987783

C -1.30075811 5.93449096 -1.20881086

C -1.26556517 4.72239452 -2.03104624

C -0.06565606 4.17104756 -2.46090492

S73

C 1.11612894 4.76155516 -2.03370100

C 1.11373046 5.97392657 -1.21138503

C -0.10327520 6.57028399 -0.83427949

C 3.27758932 5.11782321 -1.21349074

C 2.44480317 4.23527586 -2.03413686

C 2.90173819 2.99567354 -2.46148845

C 4.15417067 2.57627817 -2.03211394

C 5.01018374 3.43655083 -1.21160027

C 4.57484157 4.72151394 -0.84122734

C 5.93440709 1.30078897 -1.21034552

C 4.72199872 1.26544384 -2.03214873

C 4.17071793 0.06545383 -2.46185703

C 4.76145304 -1.11623016 -2.03467564

C 5.97402193 -1.11364068 -1.21262410

C 6.57058763 0.10341663 -0.83611861

C 5.11826111 -3.27763135 -1.21451188

C 4.23549236 -2.44501891 -2.03512045

C 2.99574510 -2.90203569 -2.46196172

C 2.57646434 -4.15436694 -2.03218144

C 3.43684035 -5.01013379 -1.21151391

C 4.72186392 -4.57464476 -0.84146440

C 1.30096367 -5.93420875 -1.20952816

C 1.26557098 -4.72205345 -2.03171070

C 0.06555445 -4.17064604 -2.46117036

C -1.11610751 -4.76116707 -2.03363045

C -1.11350196 -5.97369305 -1.21148821

C 0.10359397 -6.57020911 -0.83496200

C -3.27745719 -5.11777886 -1.21329523

C -2.44477162 -4.23498219 -2.03381230

C -2.90184637 -2.99535414 -2.46095198

C -4.15418284 -2.57605005 -2.03125761

C -5.00992046 -3.43632716 -1.21043896

C -4.57453368 -4.72146311 -0.84055103

C -5.93457865 -1.30069880 -1.20962952

C -4.72209127 -1.26526626 -2.03127609

C -4.17068407 -0.06523148 -2.46070791

C -4.76132455 1.11639855 -2.03328218

C -5.97404405 1.11376936 -1.21145553

C -6.57066653 -0.10337896 -0.83518375

C -2.64802810 6.11640633 -0.75652412

C 2.45470964 6.19892930 -0.76013319

C 6.11682465 2.64815701 -0.75887457

C 6.19932655 -2.45454909 -0.76140195

C 2.64833234 -6.11636442 -0.75793335

C -2.45437299 -6.19884130 -0.76010276

C -6.11663811 -2.64811473 -0.75777847

S74

C -6.19945340 2.45457775 -0.76017218

H -2.33054049 2.25763478 -3.02560455

H -5.34833297 5.18248601 -0.19691271

H -0.05116911 3.24508005 -3.02610242

H -0.11680119 7.43880922 -0.18552142

H 2.25690459 2.33043691 -3.02609403

H 5.18252342 5.34800450 -0.19795902

H 3.24466536 0.05082257 -3.02691050

H 7.43979460 0.11715584 -0.18827995

H 2.33032431 -2.25731241 -3.02647260

H 5.34837064 -5.18195192 -0.19785800

H 0.05090917 -3.24472979 -3.02644305

H 0.11737147 -7.43924277 -0.18689404

H -2.25718219 -2.33006132 -3.02568065

H -5.18206576 -5.34814855 -0.19733617

H -3.24453885 -0.05055436 -3.02560508

H -7.43938994 -0.11713398 -0.18670151

C -3.11638467 7.19783058 0.14288488

C -3.59132430 8.40908639 -0.40190796

C -3.09181468 7.01174360 1.54152467

C -4.03500022 9.41633168 0.46049773

C -3.54281449 8.04241726 2.37265737

C -4.01548200 9.25024649 1.84924954

H -4.40447280 10.34616242 0.03931782

H -3.52411392 7.89794732 3.44849487

C 2.88714818 7.29026620 0.14543554

C 3.33042520 8.51673703 -0.39116229

C 2.84701869 7.10190804 1.54339149

C 3.73011112 9.53618001 0.47830667

C 3.25307055 8.14515003 2.38168640

C 3.69966119 9.36618309 1.86625896

H 4.06937597 10.48015221 0.06325592

H 3.21654649 8.00125526 3.45714445

C 7.19879119 3.11680023 0.13974777

C 8.40798735 3.59579481 -0.40597164

C 7.01498195 3.08872892 1.53859589

C 9.41574213 4.03957920 0.45579727

C 8.04591268 3.54031473 2.36908572

C 9.25193880 4.01661909 1.84475642

H 10.34412244 4.41192100 0.03395017

H 7.90305763 3.51929139 3.44509750

C 7.29060683 -2.88676987 0.14435585

C 8.51483532 -3.33647520 -0.39209050

C 7.10440073 -2.83989661 1.54240314

C 9.53446685 -3.73514693 0.47770540

C 8.14776682 -3.24513033 2.38104254

S75

C 9.36675005 -3.69760321 1.86580636

H 10.47681305 -4.07911091 0.06281284

H 8.00544073 -3.20369722 3.45653311

C 3.11707617 -7.19788397 0.14116045

C 3.59590577 -8.40738599 -0.40407272

C 3.08938970 -7.01334981 1.53991107

C 4.03993414 -9.41468012 0.45807728

C 3.54118628 -8.04388329 2.37081271

C 4.01735908 -9.25015828 1.84697535

H 4.41218101 -10.34327247 0.03660926

H 3.52042724 -7.90048663 3.44675455

C -2.88674980 -7.29058111 0.14505975

C -3.33543191 -8.51486072 -0.39225918

C -2.84119203 -7.10487826 1.54328248

C -3.73455534 -9.53504979 0.47686717

C -3.24680059 -8.14878998 2.38123896

C -3.69836673 -9.36782428 1.86512112

H -4.07775227 -10.47738398 0.06131098

H -3.20623821 -8.00690608 3.45682793

C -7.19821635 -3.11665152 0.14130148

C -8.41087332 -3.58796867 -0.40356692

C -7.01065132 -3.09626733 1.53979079

C -9.41797653 -4.03229320 0.45867150

C -8.04117057 -3.54793189 2.37076193

C -9.25034741 -4.01707349 1.84730588

H -10.34887678 -4.39901159 0.03743894

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S76

H -4.01651478 9.60211190 -2.15364704

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H 3.73718985 9.72594398 -2.13631728

C 4.16807901 10.47376827 2.79427187

H 3.62668170 10.44353897 3.74549680

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H 7.85163325 4.27744137 -2.38363928

H 9.59780974 4.02567710 -2.15877868

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H 4.87075953 3.20765422 1.82730402

H 5.50335401 1.55768017 1.79275372

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C 10.37116043 4.47190657 2.76545223

H 9.96930371 4.90067505 3.68932092

H 11.01403766 3.62476580 3.03805324

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S77

H 4.89801311 -9.96684801 3.69342279

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H -3.75109482 -9.71989665 -2.13821973

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H -8.51076547 -2.61819679 -2.33765500

H -7.86072208 -4.26034736 -2.38613326

H -9.60598325 -4.00757823 -2.15521100

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H -4.86677667 -3.22604273 1.82768050

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H -5.75904225 -2.59083737 3.22752020

C -10.36878601 -4.47287046 2.76870578

H -9.96602932 -4.90656988 3.68987574

H -11.00858703 -3.62500802 3.04626000

H -10.99793072 -5.22364722 2.27970433

C -8.72140861 3.37281643 -1.89898882

H -7.98620868 4.03418662 -2.37128235

H -8.59526392 2.37599754 -2.33619032

H -9.72445884 3.73632375 -2.14148266

C -5.79156770 2.36137685 2.13120851

H -5.55997508 1.34731948 1.78640557

H -4.96425949 3.01100096 1.82268356

H -5.84038266 2.35678987 3.22421502

C -10.48177869 4.16631826 2.78641217

H -10.43596597 5.25456832 2.92348095

H -11.46559296 3.92037259 2.37310847

H -10.39444434 3.69820901 3.77211667

8MC bowl shape: KMLYP/6-31G(d,p)

C -5.97453 0.47926 -1.17080

C -4.83061 0.16386 -1.97803

C -3.95765 1.13099 -2.39430

C -4.17743 2.41548 -1.96033

C -5.33047 2.77072 -1.18344

S78

C -6.24348 1.81473 -0.82013

C -3.89960 4.55429 -1.14760

C -3.29851 3.50541 -1.93403

C -1.98761 3.56279 -2.33497

C -1.24047 4.62202 -1.89877

C -1.81034 5.70208 -1.13288

C -3.14097 5.68937 -0.79871

C 0.46925 5.95223 -1.10877

C 0.15251 4.77324 -1.87841

C 1.11799 3.89211 -2.28386

C 2.39961 4.12192 -1.85728

C 2.76283 5.29178 -1.09189

C 1.79839 6.22873 -0.76802

C 4.56223 3.86662 -1.11998

C 3.49434 3.25233 -1.86979

C 3.55359 1.95065 -2.29047

C 4.63165 1.20718 -1.88820

C 5.71306 1.77669 -1.11909

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C -1.15488 -3.95522 -2.41548

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C -5.15358 4.12151 -0.73924

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C 4.11320 5.13780 -0.70767

S79

C 6.54577 0.73074 -0.71697

C 5.14126 -4.10284 -0.72183

C 0.73471 -6.52842 -0.72372

C -4.09013 -5.11706 -0.70134

C -6.53154 -0.71491 -0.71773

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C 8.99358 0.56110 -0.42417

C 7.63432 1.21478 1.45586

C 10.11358 0.67597 0.37012

C 8.78135 1.31498 2.21827

C 10.02840 1.05216 1.69532

H 11.08209 0.47048 -0.05998

H 8.69361 1.60091 3.25532

C 4.89987 6.08319 0.08591

C 4.62448 6.27487 1.43642

C 5.95000 6.77702 -0.51116

C 5.38687 7.17102 2.15831

C 6.68601 7.66507 0.24357

C 6.41583 7.88155 1.57914

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H 7.49401 8.20492 -0.22633

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C -1.08026 8.96986 -0.45015

C -0.82394 7.60148 1.51573

C -1.21917 10.07575 0.36222

C -0.96735 8.73080 2.29534

C -1.16096 9.97685 1.73689

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S80

C -7.29363 5.31743 -0.44935

C -5.83834 5.05148 1.45414

C -8.18431 5.99840 0.35170

C -6.75961 5.73442 2.22290

C -7.93622 6.21610 1.69169

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H -6.55097 5.88865 3.27054

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C -7.59540 -0.47167 1.50573

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C -8.70176 -0.61926 2.31861

C -9.95546 -1.51196 0.52060

C -9.89114 -1.12813 1.84488

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H -10.87646 -1.91922 0.13233

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C -4.43387 -6.12296 1.53525

C -5.90085 -6.74128 -0.27787

C -5.14098 -6.97213 2.36272

C -6.57376 -7.58288 0.58077

C -6.20651 -7.71579 1.90444

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H -7.41018 -8.15184 0.20466

C 0.84709 -7.68903 0.16087

C 1.15495 -7.51692 1.50689

C 0.62275 -8.96616 -0.34657

C 1.24510 -8.62981 2.31871

C 0.72948 -10.05062 0.49703

C 1.04443 -9.90364 1.83255

H 1.47322 -8.49350 3.36470

H 0.56201 -11.03973 0.09903

C 6.05134 -4.85761 0.14062

C 6.77494 -5.92478 -0.38609

C 6.18340 -4.52302 1.48485

C 7.63014 -6.62669 0.43527

C 7.04797 -5.25500 2.27421

C 7.77980 -6.30784 1.76967

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H 7.14652 -4.99546 3.31714

C -1.27964 11.18818 2.59468

H -1.69253 10.94502 3.56784

H -0.30721 11.64580 2.75964

H -1.91596 11.93736 2.13575

C -0.62621 6.26735 2.14838

H -1.41474 5.57554 1.86374

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S81

H -0.61754 6.34653 3.22948

C -1.14671 9.10462 -1.93177

H -0.23107 8.75290 -2.39820

H -1.95687 8.50994 -2.34428

H -1.30154 10.13733 -2.22272

C 6.27319 6.57447 -1.95120

H 6.64069 5.56916 -2.13727

H 5.39274 6.70502 -2.57312

H 7.03132 7.27642 -2.27950

C 3.54804 5.50175 2.11680

H 2.56073 5.84255 1.81757

H 3.60376 4.44690 1.86489

H 3.62316 5.60250 3.19363

C 6.30755 1.47465 2.08332

H 5.89460 2.43172 1.77579

H 5.58383 0.71726 1.79815

H 6.39056 1.48039 3.16430

C 9.12992 0.16228 -1.85310

H 8.68162 -0.80968 -2.03952

H 8.62674 0.86804 -2.50708

H 10.17354 0.11170 -2.14208

C 11.25027 1.14115 2.54149

H 11.08584 1.77187 3.40821

H 11.54803 0.15983 2.90291

H 12.08837 1.54658 1.98399

C 5.39138 -3.41316 2.08703

H 5.76036 -2.43875 1.77836

H 4.35007 -3.46295 1.78308

H 5.43407 -3.45664 3.16935

C 6.64909 -6.29193 -1.82460

H 5.65503 -6.66431 -2.05530

H 6.81606 -5.43125 -2.46536

H 7.36575 -7.06005 -2.09156

C 0.28745 -9.16586 -1.78457

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H 1.01583 -8.68232 -2.42874

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H 0.59758 -5.46347 1.74574

H 1.32337 -6.19780 3.17063

C 1.18240 -11.09229 2.71811

H 0.49141 -11.87920 2.43488

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H 0.99655 -10.83667 3.75556

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S82

H -6.74421 -5.65162 -1.91906

H -5.48864 -6.76940 -2.37688

H -7.08025 -7.37464 -1.93641

C -3.30692 -5.32133 2.09283

H -2.34135 -5.75672 1.84885

H -3.30553 -4.31060 1.69826

H -3.37764 -5.26644 3.17318

C -6.32531 0.05848 2.07890

H -5.46522 -0.49235 1.71237

H -6.16695 1.10104 1.81565

H -6.33886 -0.00850 3.16080

C -8.98683 -1.80611 -1.74935

H -8.68054 -1.00774 -2.41872

H -8.34862 -2.65744 -1.96801

H -10.00724 -2.08017 -1.99112

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H -7.72477 4.05904 -2.12742

H -8.49806 5.63534 -2.17983

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H -4.37415 3.51971 1.75446

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C -8.92864 6.92554 2.54506

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H 7.18814 8.63363 3.42540

S83

8MC s-shaped transition state: UB3LYP/6-31G(d,p)

C 5.38099 -3.06970 -0.07552

C 4.32006 -2.19055 0.38201

C 3.01375 -2.59576 0.52693

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C -6.15219 0.83159 0.08742

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C -2.73380 3.91139 -0.24319

C -3.74939 4.90590 0.04981

C -5.08711 4.45643 0.23235

C -1.61938 5.94007 0.02078

C -1.46700 4.50527 -0.14582

C -0.25673 3.85865 -0.05317

C 0.86074 4.64875 0.08140

C 0.83089 6.09784 -0.01167

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C 3.07628 5.34591 -0.03828

C 2.19085 4.21811 0.18781

C 2.63234 2.94397 0.45490

C 3.98563 2.71942 0.35411

C 4.93244 3.73753 -0.06472

C 4.46503 5.07832 -0.19701

C 5.99083 1.62008 -0.08276

C 4.63077 1.47235 0.40057

C 4.05374 0.25922 0.69286

S84

C 4.79140 -0.86720 0.41454

C 6.15219 -0.83159 -0.08742

C 6.75568 0.43996 -0.30727

C 3.03580 -6.15432 -0.15737

C -2.21059 -6.49650 0.10999

C -6.16122 -3.03252 0.31375

C -6.50211 2.20687 0.33713

C -3.03580 6.15432 0.15737

C 2.21059 6.49650 -0.10999

C 6.16122 3.03252 -0.31375

C 6.50211 -2.20687 -0.33713

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H 7.07514 3.49293 -0.67262

H 2.55093 7.51820 -0.23722

H -3.50028 7.11697 0.34036

8MC bowl shape: (U)KMLYP/6-31G(d,p) C -5.97626 0.45232 -1.16811

C -4.83056 0.14195 -1.97491

C -3.96159 1.11323 -2.39097

C -4.18705 2.39608 -1.95635

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C -6.25093 1.78664 -0.81726

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C -3.31289 3.49041 -1.93089

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S85

C 0.13127 4.77461 -1.87834

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C 2.38123 4.133 -1.85762

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C 1.77078 6.23782 -0.76893

C 4.54482 3.88681 -1.11976

C 3.47995 3.26792 -1.86975

C 3.54503 1.96668 -2.29083

C 4.62623 1.22794 -1.88827

C 5.70483 1.8021 -1.11901

C 5.67781 3.16189 -0.79484

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H 6.7593 9.89949 2.25328

H 7.1508 8.66165 3.42766

Macrocyclic Polyradicaloids with Unusual Super-ring ......Gopalakrishna, Hoa Phan, Naoki Aratani,...

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Transcript of Macrocyclic Polyradicaloids with Unusual Super-ring ......Gopalakrishna, Hoa Phan, Naoki Aratani,...