Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 8, pp. 1442−1446.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
N.M. Geller, A.G. Ivanov, V.V. Shamanin, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 8, pp. 1342−1346.
AND POLYMERIC MATERIALS
New Germanium- and Tin-Containing
Polysalicylideneazomethines Derived from Tetraamines
N. M. Geller, A. G. Ivanov, and V. V. Shamanin
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received March 23, 2009
Abstract—Polysalicylideneazomethines containing Ge and Sn atoms in the polymeric chain were prepared
by polycondensation of N,N',N'',N'''-tetrasalicylidene-3,3',4,4'-tetraaminodiphenyl ether with germanium or
tin tetrachloride or tetraethoxide. Spectroscopic examination showed that the polymers exhibit nonclassical
polyconjugation and belong to a new class of semiconductor polytransannular-conjugated polymers.
Previously by polycondensation of N,N',N'',N'''-
tetrasalicylidene -3,3',4,4'-tetraaminodiphenyl ether
(TSDPE) and N,N',N'',N'''-tetrasalicylidene-3,3',4,4'-
tetraaminodiphenyl (TSDP) with silicon tetrachloride we
prepared polytetrasalicylideneazomethines with Si atoms
in the backbone: catena-poly[silicon(μ-N,N',N'',N'''-
O'',N'',O''',N''')] and catena-poly[silicon(μ-N,N’,N'',N'''-
O,N,O',N':O'',N'',O''',N''')] [1, 2]. We found that the
Si-containing polymers, despite break of the conjugation
chain (presence of Si–O–Si bonds), are electroactive
This fact was accounted for from the standpoint
of nonclassical electron density delocalization.
This concept, applied previously to interpretation
of properties of organometallic polymeris such as
poly(dialkylsilyl-p-xylylidenes) [3, 4], consists in
assuming formation of a “nonclassical” conjugation
system in the polymer by donor–acceptor interaction
of valence shells of the heteroatoms (metalloid and
nitrogen) separated by a nonconjugated fragment (e.g.,
methylene group). The backbone of silicon-containing
polymers also contains both donor (nitrogen atoms
of azomethine bond) and acceptor (Si) atoms, which
creates prerequisites for the formation of intramolecular
donor–acceptor charge-transfer complexes (CTCs).
Such a transannular donor–acceptor (DA) interaction
should be accompanied by efﬁ cient charge transfer
from the donor to the acceptor, which will lead to
polarization of the polymer and hence impart to it
electro- and photophysical properties.
As this study is a logical continuation of the previous
studies, it seemed interesting to synthesize and examine
polymers of similar structure but containing the Ge and
Sn atoms as chemical analogs of Si:
In synthesis of the polymers, we used as comono-
tetraaminodiphenyl ether (М1)