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Hydrogen-Bonded Self-assembly of Supramolecular Donor–Acceptor Complexes of (E)-Bis(18-crown-6)azobenzene with Bis(ammoniopropyl) Derivatives of Bipyridine and Dipyridylethylene in Acetonitrile

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Abstract

The supramolecular complex formation between donor (E)-bis(18-crown-6)azobenzene ((E)-1) and bis(ammoniopropyl) derivatives of bipyridine and dipyridylethylene acceptors (2, (E)-3) was studied in MeCN using steady-state absorption and fluorescence spectroscopy, fluorescence kinetics, and quantum-chemical (DFT, TDDFT, QDPT) calculations. The complexes are quite stable, but they undergo decomposition via substitution by alkali and alkaline-earth metal cations. The formation of 1:1 and 1:2 complexes between (E)-1 and alkali and alkaline-earth metal cations (Mn+) was confirmed. Spectral-kinetic parameters and stability constants were calculated. The determined stability constants are generally lower than those for bis(crown)stilbene complexes due to moderate electron-donor ability of azobenzene. The plot of fluorescence quantum yields of 1·(Mn+)2 vs charge density of the metal cation shows two separate linear relations for unipositive and dipositive ions. The results of quantum-chemical calculations supported the conclusions derived from steady-state experiments. The most stable conformations of pseudocyclic complex (E)-1·2 and two metal complexes were found. The latter involve 4 or 6 molecules of acetonitrile per each complex: (E)-1·(Ca2+)2·(MeCN)4, (E)-1·(K+)2·(MeCN)6. Based upon quantum-chemical calculations of model species, the character of absorption bands of crowns and their complexes with actual energy conversion pathway are discussed.

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Acknowledgements

This research was done in frames of project funded by the Russian Science Foundation (Project No. 22-23-00161), except synthesis of (E)-bis(18-crown-6)azobenzene and bis(ammoniopropyl) derivatives of bipyridine and dipyridylethylene. Synthesis of the (E)-bis(18-crown-6)azobenzene and bis(ammoniopropyl) derivatives was done in a framework of project No. 22-13-00064 of the Russian Science Foundation.

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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory 1-3, Moscow, 119991, Russian Federation

    Valery V. Volchkov, Mikhail N. Khimich, Mikhail Ya. Melnikov & Sergey P. Gromov

  2. N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina Str. 4, Moscow, 119991, Russian Federation

    Mikhail Ya. Melnikov

  3. N. M. Emmanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina Str. 4, Moscow, 119334, Russian Federation

    Anton E. Egorov

  4. FSRC “Crystallography and Photonics”, Photochemistry Center of RAS, Russian Academy of Sciences, Novatorov Str. 7A-1, Moscow, 119421, Russian Federation

    Roman O. Starostin, Alexandra Ya. Freidzon, Svetlana N. Dmitrieva & Sergey P. Gromov

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V. Volchkov - steady-state measurements, writing the manuscript, editing M. Khimich, R. Starostin, and A. Freidzon - quantum-chemical calculations, writing the quantum-chemical paragraph A. Egorov - measurements of fluorescence kinetics S. Dmitrieva, R. Starostin - organic synthesis M. Melnikov, S. Gromov - reviewing the manuscript

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Correspondence to Valery V. Volchkov.

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Volchkov, V.V., Khimich, M.N., Melnikov, M.Y. et al. Hydrogen-Bonded Self-assembly of Supramolecular Donor–Acceptor Complexes of (E)-Bis(18-crown-6)azobenzene with Bis(ammoniopropyl) Derivatives of Bipyridine and Dipyridylethylene in Acetonitrile. J Solution Chem 52, 805–822 (2023). https://doi.org/10.1007/s10953-023-01271-6

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