Kirill P. Birin, Yulia G. Gorbunova, Aslan Yu. Tsivadze Lviv, 2010.
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Transcript of Kirill P. Birin, Yulia G. Gorbunova, Aslan Yu. Tsivadze Lviv, 2010.
Kirill P. Birin, Yulia G. Gorbunova, Aslan Yu. Tsivadze
Lviv, 2010
Heteroleptic lanthanide (porphyrinato)(phthalocyaninates) as promising starting materials for development of molecular information storage devices.
J. Org. Chem. 2000, 65, 7379-7390J. Mater. Chem., 2002, 12, 808–828Inorg. Chem. 2006, 45, 5479-5492, etc.
4 stable redox states!6 stable redox states!
Multi-step complicated synthesis…
N
N
N
N
R
R
R
R
R'
R'
CN
CN
N N
NN
R
R
R
R
N N
NN
R
R
R
R
NN
N
NN
NN
NR'
R'
R'R'
R'R'
R'R'
Ln
Ln
H
H
Ln(acac)3, DBU
reflux, 24h, 160oC
K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.
N
N
N
N
R
R
R
R
H
HLn(acac)3
NN
NN
R
R
R
R
LnO O
R'
R'
CN
CN
NN
NN
R
R
R
R
LnO O
DBU
N N
NN
R
R
R
R
NN
N
NN
NN
NR'
R'
R'R'
R'R'
R'R'
Ln
Stage 1
Stage 2
K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.
N N
NN
R
R
R
R
N N
NN
R
R
R
R
NN
N
NN
NN
NR'
R'
R'R'
R'R'
R'R'
Ln
Ln
NN
NN
R
R
R
R
LnO O
N N
NN
R
R
R
R
NN
N
NN
NN
NR'
R'
R'R'
R'R'
R'R'
Ln+
Single isomer of triple-decker complex!
Stage 3
K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.
(Pc)Y(An4P)61% of HOMO is localized at Pc-ligand
((MeO)8Pc)Y(An4P)66% of HOMO is localized at Pc-ligand
Extended Huckel calculation of HOMO of MM+ optimized molecule of double-decker complex for explanation of selectivity
K.P. Birin et al. J. Porphyrins Phthalocyanines, 2009, 13, № 2, 283-290.
N
N
N
N
R
R
R
R
H
H
R'
R'
CN
CN
R= corresp. porphyrin
H TPPH2
OMe An4PH2
Br Br4TPPH2
R’= corresp. phthalocyanin
e
H PcH2
OMe (MeO)8PcH2
OBu (BuO)8PcH2
fused 15-crown-5
(15C5)4PcH2Ln(acac)3 Ln=La-Eu
H OMe OBu (15C5)
H Nd
Br Nd Nd Nd La, Nd, Eu
OMe Nd La-Eu
Triple-decker complexes are obtained for the whole La-Eu
series
Synthesis is independent from porphyrin meso-substituents
Only double-decker complexes are obtained.
Crucial influence of electron-donating substituents in Pc-
macroycle
Porphyrinmeso-substituents
Phthalocyaninesubstituents
All synthesized complexes are characterized with: MALDI-TOF mass-spectrometry
UV-Vis spectroscopy
1H- and 13C-NMR
N
N
NO O
OOO
HPcH-CrH-Cr
H-Cr
H-Cr
OMeN
Hoi Hmi
HmoHoo
HPyrr
La
OMeN
Hoi Hmi
HmoHoo
HPyrr
La
NMR of [An4P]La[(15C5)4Pc]La[An4P]
H H
H H
H H
H H
Por
Por
Pc
Por
Pc
K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
NMR of [An4P]La[(15C5)4Pc]La[An4P] and [Br4TPP]La[(15C5)4Pc]La[Br4TPP]
N
N
NO O
OOO
HPcH-CrH-Cr
H-Cr
H-Cr
XN
Hoi Hmi
HmoHoo
HPyrr
La
XN
Hoi Hmi
HmoHoo
HPyrr
La
X = BrX = OMe
NMR of series of [An4P]Ln[(15C5)4Pc]Ln[An4P] complexesLanthanide-induced paramagnetic shifts complicate the spectra
N
N
NO O
OOO
HPcH-CrH-Cr
H-Cr
H-Cr
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln1
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln2
K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
LIS results from magnetic interaction between f-electrons of lanthanide and observed nuclei
LIS: = para – dia
In turn, two mechanisms are possible for interaction:through-bond, or contact (con)through-space, or dipolar (dip)
LIS is a function of molecular structureFinally, LIS is considered as = con + dip
Ln CC
CC
Hi
contact contribution
dipolar contributionC. Piguet, C.F.G.C. Geraldes. Handbook on the physics of rare earths, vol. 33, ch. 215, 353-463.
Contact contribution is presumed to be negligible if lanthanide and observed nuclei is separated by 5 or more -bonds
Dipolar contribution is bound to geometry of the molecule and decreases as 1/R3, where R – distance between lanthanide and nuclei
Contact and dipolar terms for each lanthanide ion are tabulated values, designated as <Sz>Ln and DLn, respectively
= Fi<Sz>Ln + A20GiDLn
3
2 13R
CosGi
If more than one lanthanide center is present, resulting LIS is a combination of contributions.
N
N
NO O
OOO
HPcH-CrH-Cr
H-Cr
H-Cr
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln1
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln2
In order to explain the particular behavior of each peak in spectra upon LIS, MM+ calculation of structure of complex was performed. Averaged coordinates of protons are plotted with Gi-diagram
K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
Two opposite aims:Explanation of features of NMR spectra from
structural parameters of moleculesDetermination of structural parameters of molecules
in solution from features of NMR spectra
Utilization of dipolar contribution of LIS as structural probe
Separation of contact and dipolar contributions is unavoidable
Separation of contributions of LIS is possible through statistical analysis of series of NMR datasets for isostructural complexes
Model compounds [An4P]Ln[(15C5)4Pc]Ln[An4P]
Ln=La-Eu, 5 paramagnetic lanthanides and La complex as diamagnetic reference
First step is verification of isostructurality of the series of compounds.
Datasets for all types of protons in the molecule are plotted in Hi/<Sz>Ln vs Hj/<Sz>Ln coordinates. Linearization equation is
Lnz
Lnjijijji
Lnz
Lni
SRRFF
S,,
Fine linearization of datasets testifies the isostructurality of the whole series of compounds.
K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
Next step is separation of contact and dipolar contributions
Datasets are plotted as Hi/<Sz>Ln
and their linearization is performed according to equation
Here the slope of gives the value of dipolar term and intercept corresponds to contact term.
Lnz
Lnii
Lnz
Lni
S
DGAF
S02
,
Finally, tables of contact and dipolar contributions of LIS for each proton of each complex are obtained.
K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
Starting point for structure determination – coordinates of protons of (15C5)4Pc-ligand in symmetrical environment
[Pc]Sm[(15C5)4Pc]Sm[Pc]
A. G. Martynov et al. Eur. J. Inorg. Chem., 2007, 30, 4800.K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
Determination of lanthanides positions
LnLn
2
2
EXPk
EXPi
EXPk
EXPi
TEORk
TEORi
GG
GG
GG
AF
Ln…Ln = 3.886A
K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
Determination of positions of porphyrin decks
Coordinates of protons of porphyrin deck are obtained from MM+ optimization of
molecular geometry
K.P. Birin et al. Magn. Reson. Chem., 2010, 48, 505-515.
Ln
Ln
Pc...Por = 3.395 Å
Finally, protons of the molecule are located and may act as binding points for the whole structure
The described procedure allows determination of structural parameters of complexes in solutions
Ln...Ln = 3.886 Å
Pc...Por = 3.395 Å
Ln...N4(Pc) = 1.943 Å
Ln...N4(Por) = 1.453 Å
ms-An skew = 41o
N
N
NO O
OOO
HPcH-CrH-Cr
H-Cr
H-Cr
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln1
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln2
Further refinement of structure needs application of LIS data for carbon atoms of molecular skeleton.
13C{H} spectra of triple-decker complexes [An4P]Ln[(15C5)4Pc]Ln[An4P]
Ln = LaLn = Nd
Assignment of 13C-NMR spectra is possible in several ways:
INEPT and DEPT techniques to determine signals of C, CH, CH2 and CH3 fragments
Heteronuclear 13C-1H COSY to correlate directly bound 1H and 13C atoms
Pulse-field gradient techniques:HMQC – to correlate directly bound 1H and 13C atomsHMBC – to correlate 1H and quaternary 13C atoms
HMQC 13C-1H correlation of triple-decker complexes [An4P]Ln[(15C5)4Pc]Ln[An4P]
Ln = NdLn = La
N
N
NO O
OOO
HPcH-CrH-Cr
H-Cr
H-Cr
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln1
OMeN
Hoi Hmi
HmoHoo
HPyrr
Ln2
Proton dimensionCarb
on
dim
en
sio
n
Application of 13C data for structure determination allows to operate with most atoms of molecular core, except quaternary carbons.
The developed methodology for structural analysis of heteroleptic porphyrinato-phthalocyaninates in current state:
Allows precise determination of relative positions of atoms of molecule
Involves all protons of the molecule and most carbon atoms of molecular core
Allows to determine structural parameters of molecule in solution
This work was supported by
Russian Foundation for Basic Research (grant#08-03-00835) and programs of Russian Academy of Sciences.
Thank you for your attention!