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!