Donor-acceptor molecular oligogermanes:
Novel properties and structural aspects
Kirill V. Zaitsev a* , Anastasia V. Kharcheva a , Kevin Lam b , Zhaisan Zhanabil c , Guldana
Issabayeva c , Yuri F. Oprunenko a , Andrei V. Churakov d , Galina S. Zaitseva a ,
Sergey S. Karlov a
a
b
Department of Chemistry, Moscow State University
Department of Pharmaceutical, Chemical and Environmental Sciences, University of Greenwich
c
Department of Chemistry, Nazarbayev University, Astana, Kazakhstan
d
N.S. Kurnakov General and Inorganic Chemistry Institute, Russian Academy of Sciences
Email: [email protected], [email protected]
Abstract
In recent years, the scope of reactivity of Group 14 (Si, Sn and Ge) elements has been
extensively broadened via studying their catenated derivatives. However, among the Group 14
elements, the “structure - property” relationships of Ge derivatives were only superficially
explored. It was found that the physical properties of the oligogermane molecules strongly
depend on the nature of the substituents, their spatial geometry, the number of Ge atoms in the
chain and the overall conformation of the molecules themselves. The investigated compounds
of oligogermanes were prepared through improved and simplified synthetic procedure
involving hydrogermolysis as a terminal step of the synthesis. The novelty of the proposed
synthesis was appeared in the formation of linear oligogermyl amide, Ph 3 GeGeMe 2 NMe 2 ,
which was a crucial starting material for the generation of desired oligogermane molecules,
Ph 3 GeGeMe 2 Ge(C 6 F 5 ) 3 and [Ph 3 GeGeMe 2 ] 2 Ge(C 6 F 5 ) 2 , containing electron donor (Me, Ph) and
acceptor (C 6 F 5 ) groups. The molecular structures of these compounds were studied by XRD. It
was, also, shown that in a crystal, the molecule of Ph 3 GeGeMe 2 Ge(C 6 F 5 ) 3 formed wide
channels, in which the solvated nonpolar n-hexane molecule was present. The NMR ( 1 H, 13 C
and 19 F), optical (UV/vis absorption, luminescence) and electrochemical (cyclic voltammetry)
properties of both compounds were widely investigated.
Donor-Acceptor
oligogermanes
(C 6 F 5 ) 2 GeH 2
Ph 3 Ge-Ge(NMe 2 )
Me 2
(C 6 F 5 ) 3 GeH
Hydrogermolysis
Ph 3 Ge
Me 2 Me 2
Ge Ge
Ge (C 6 F 5 ) 3
Ph 3 Ge
Me 2
Ge
Ge
(C 6 F 5 ) 2
GePh 3
UV-Vis absorption
Electrochemical oxidation
Luminescence
Reference
1. K.V. Zaitsev, A.V. Kharcheva, K. Lam, Zh. Zhanabil, G. Issabayeva, Y.F. Oprunenko, A.V. Churakov,
G.S. Zaitseva, S.S. Karlov. J. Organomet. Chem. 867 (2017) 228-237.