Donor–acceptor chromophores based on coordination polymers of silicon(IV) and germanium(IV)

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New charge-transfer complexes with pyrazine are synthesized from germanium(IV) and silicon(IV) bis(catecholates): 36Сat2Ge, 35Cat2Ge, and 36Сat2Si (36Сat and 35Cat are 3,6- and 3,5-di-tert-butylpyrocatechol dianions, respectively). The synthesized compounds in the crystalline state are 1D coordination polymers with the octahedral environment of the complexing agent. The electronic absorption spectra of suspensions of the crystalline compounds in Nujol demonstrate an absorption in a range of 450–800 nm causing their intense color. A set of the spectral and theoretical studies indicates that the synthesized metal-organic frameworks of silicon and germanium can be considered as donor–acceptor chromophores with the photoinduced interligand charge transfer between the donor catecholate and acceptor pyrazine ligands.

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K. Arsenyeva

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: kselenia22@gmail.com
俄罗斯联邦, Nizhny Novgorod

A. Klimashevskaya

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: kselenia22@gmail.com
俄罗斯联邦, Nizhny Novgorod

A. Maleeva

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: kselenia22@gmail.com
俄罗斯联邦, Nizhny Novgorod

K. Pashanova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: kselenia22@gmail.com
俄罗斯联邦, Nizhny Novgorod

I. Yakushev

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: kselenia22@gmail.com
俄罗斯联邦, Moscow

P. Dorovatovskii

National Research Center Kurchatov Institute

Email: kselenia22@gmail.com
俄罗斯联邦, Moscow

A. Piskunov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: kselenia22@gmail.com
俄罗斯联邦, Nizhny Novgorod

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2. Fig. 1. Molecular structure of the [35Cat2GePz]x (III) (left) and [36Сat2SiPz]x (I) (right) units. Thermal ellipsoids of 30% probability are shown for key atoms. Hydrogen atoms are not shown for clarity.

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3. Fig. 2. Fragment of the crystal packing of coordination polymers III (left) and I (right). Thermal ellipsoids of 30% probability are shown for key atoms. The tert-butyl substituents are represented by the first quaternary carbon atom, and hydrogen atoms are not shown for clarity.

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4. Fig. 3. UV-visible spectra of coordination polymers I–III in DMF solution at 298 K, solution concentration c = 5 × 10–4 mol/l.

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5. Fig. 4. Electronic absorption spectra of suspensions of coordination polymers I–III, recorded at 298 K in vaseline oil.

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6. Fig. 5. View of the boundary orbitals of complex II.

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7. Scheme 1

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