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Supporting Information-ICatalytically Active Lead-Imidazolium Coordination Assemblies with Diversified Lead(II)

Coordination Environments

Chatla Naga Babu,a Paladugu Suresh,a Katam Srinivas,a Arruri Sathyanarayana,a Natarajan Sampathb and Ganesan Prabusankara*

a Department of Chemistry, Indian Institute of Technology Hyderabad, ODF Campus, Yeddumailaram, Telangana, INDIA-502 205. Fax: +91 40 2301 6032; Tel: +91 40 2301 6089; E-mail: prabu@iith.ac.in b School of Chemical and Biotechnology, SASTRA University, Tirumalaisamudram, Thanjavur, Tamil Nadu, INDIA-613 401.

C:\Program Files (x86)\OPUS_65\MEAS\.1937 GP-NB-S-185 SOLID 08/11/2013

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Figure S1. FT-IR spectrum of 1

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016

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Figure S2. FT-IR spectrum of 2.

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100015002000250030003500Wavenumber cm-1

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Page 1/1Figure S3. FT-IR spectrum of 3.

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Page 1/1Figure S4. FT-IR spectrum of 4.

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Figure S5. FT-IR spectrum of 5.

4

Figure S6. 1H NMR spectrum of 2.

5

Figure S7. 13C NMR spectrum of 2.

6

Figure S8. 1H NMR spectrum of L2H2Br2.

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Figure S9. 13C NMR spectrum of L2H2Br2.

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Figure S10. Coordination mode of lead centres in 3.

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Although complexes 4 and 5 were isolated from same starting materials, 4 was isolated after 12 h and 5 was isolated after 48 h. We never isolated 4 and 5 together under any of these (vide supra) reactions. In order to prove this, we have performed the PXRD for the bulk sample and compared with simulated PXRD peaks of single crystal X-ray data (using mercury software). The experimental PXRD matches very well with simulated PXRD, which clearly supports the purity of bulk sample (purity is on par with single crystal). We assume that the comparison of PXRD is more appropriate than elemental analysis (as reported in MOF chemistry).

Figure S11. (a) PXRD of 4 (simulated in green, experimental in red); (b) PXRD of 5 (simulated in green, experimental in blue).

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Similarly, as shown below the experimental PXRD of 1 matches very well with its simulated PXRD.

Figure S12. PXRD of 1 (simulated in green, experimental in red)

In addition, the experimental PXRD of 3 matches very well with its simulated PXRD.

Figure S13. PXRD of 3 (simulated in red, experimental in blue)

400 450 500 550 600 650 700

Inte

nsity

Wavelength, nm

438434 (1)(LH)

Figure S14. Solid state emission spectrum of 1 compared with LH

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400 450 500 550 600 650 700 750

Inte

nsity

Wavelength, nm

437

436(L1H2Br2)

(2)

Figure S15. Solid state emission spectrum of 2 compared with L1H2Br2.

400 450 500 550 600 650 700 750

Inte

nsity

Wavelength, nm

436

435(L2H2Br2)

(3)

Figure S16. Solid state emission spectrum of 3 compared with L2H2Br2.

12

400 450 500 550 600 650 700

Inte

nsity

Wavelength, nm

437

434

425

(L3HCl)

(4)

(5)

Figure S17. Solid state emission spectrum of 4, 5 compared with L3HCl.

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Table S1: Selected examples of NHC (organocatalyst) mediated benzoin condensation reaction

Ph

O

H Base

O

Ph

Ph

OH

NHC

Entry Isolated yield

Time Catalyst Reference

1 33-83% 16 h

N

N

N

O

Ph

t-Bu

BF4

Enders D, Niemeier O and Henseler A Chem. Rev., 2007, 107, 5606-5655

2 22-72 % 60 h

N

N

NPh

OO

Ph

CH3H3C

ClO4

Enders D, Niemeier O and Henseler A Chem. Rev., 2007, 107, 5606-5655

3 0-33% 48 h

N

HN

NNPh

Ph O

ClO4

N

NNPh

ROPh

PhBF4

Louise Baragwanath, Christopher A. Rose, Kirsten Zeitler, and Stephen J. Connon, J. Org. Chem. 2009, 74, 9214–9217

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4 33-90 % 16 h

N

N

N

OCH3

H3C CH3

Dieter Enders and Ulrike Kallfass, Angew. Chem. Int. Ed. 2002, 41, 1743-1745

5 72-95 % 20 h

N

N

NN

N

N

Ar

Ar

X

X

N

N

NN

N

N

Ar

Ar

X

X

Satyanarayana A and Prabusankar G, J. Chem. Sci., 2015, 127, No. 5, pp. 821–831

6 72-82 % 22 h

NSClO4

Isabel Piel, Marius D. Pawelczyk, Keiichi Hirano, Roland Fröhlich, and Frank Glorius, Eur. J. Org. Chem. 2011, 5475–5484

7 27-98 % 20 h

N NN

NNN

OO

R1 R1

2 X

Yajun Ma, Siping Wei, Jie Wu, Fei Yang, Bo Liu, Jingbo Lan,Shengyong Yang, and Jingsong You, Adv. Synth. Catal. 2008, 350, 2645 – 2651

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Table S2: Catalysts 1-5 mediated benzoin condensation of 4-nitrobenzaldehyde in 12 h.

NN

NO

R1

Cl

Isolated Yield(%)Entry Catalyst

First run Second run Third run

1 1 98.75 96.88 97.21

2 2 94.90 96.10 96.74

3 3 91.25 93.43 89.78

4 4 95.10 97.95 94.76

5 5 89.87 87.65 90.65

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Table S3: Selected examples of insitu N-Heterocyclic Carbene mediated benzoin condensation of 4-nitrobenzaldehyde.

O

H

O

OH

NO2

O2N

O2N

NHC

Entry Isolated Yield, %

Time Catalyst Reference

1 27 24 h

SN

NN

NH2

OPOP

HO

O

OH

O

OH

Cl

Hernandez, Karel et al

Chemistry - A European Journa.l, 2015, 21(8), 3335-

3346.

2 34 20 sec

SN

NN

NH2

HO

Cl

Bag, Seema et al, Journal of Chemical Research., 2006, 4,

267-269.

3 85 12 h N

N

N

S

2Br

Mohanazadeh, Farajollah and Aghvami, Majid, Phosphorus,

Sulfur and Silicon and the Related Elements., 2007,

182(10), 2467-2475.

4 0 20 h

N

N (CH2)11

(CH2)11

CH3

CH3

Br

Iwamoto, Ken-ichi et al

Tetrahedron Letters., 2006, 47(40), 7175-7177.