International Summer School PROGRAM - Laboratoire d'Infochimie ...

Synthesis and supramolecular association of heteroleptic
terbium (porphyrinato)(crownphthalocyaninates)
Birin K.P. , Kamarova K.A., Gorbunova Yu.G., Tsivadze A.Yu.
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS
N.S. Kurnakov Institute of General and Inorganic Chemistry RAS
Leninsky pr., 31, Moscow, Russia, 119991.
E-mail: yulia@igic.ras.ru, kirill.birin@gmail.com
Sandwich type lanthanide complexes with porphyrins and phthalocyanines are
attractive as rigid cores for development of selective receptors. Modification of
compounds with crown-ether moieties allows binding of alkali cations and formation of
supramolecular architectures. The only one paper is devoted to design of such type of
heteroleptic receptors, - europium (porphyrinato)((15-crown-5)-phthalocyaninates) [1].
In present work we report on the synthesis of alkali cations receptors based on terbium
triple-decker (porphyrinato)((15-crown-5)-phthalocyaninates).
[Br4TPP]Tb[(15C5)4Pc]Tb[Br4TPP] (1) [Br4TPP]Tb[(15C5)4Pc]Tb[(15C5)4Pc]
(2)
The triple-decker terbium complexes Tb2[Br4TPP]2[(15C5)4Pc]
(1) and
Tb2[Br4TPP][(15C5)4Pc]2 (2) were synthesized by interaction of terbium
monoporphyrinate with double-decker compounds with yields of 48% and 63%,
respectively. The spectrophotometric titration of the heteroleptic triple-deckers with
K[BPh4] revealed that receptor 1 is unable to bind K +
because of sterical hindrances.
The unsymmetrical complex 2 shows hypsochromic shift of absorption bands upon
titration, which can be attributed to formation of supramolecular dimers, similar to [1].
Acknowledgements. The authors are grateful to Foundation of Russian President
for support of young scientists (grant MK-212.2010.3), RFBR (grant 11-03-00968) and
Russian Academy of Sciences for financial support.
1. M. Bai, M. Bao, C. Ma, et al. J. Mater. Chem. 2003, 13 (6), 1333-1339.