MS37-P01 Photoinitiated solid-state [2+2] cycloaddition reaction in [Zn2(H2O)2(2-Amal)2(bpe)] (2-Amal = 2-ALLYLMALONATE) CRYSTAL Alexander Volodin (A.N. Nesmeyanov Institute of Organoelement Compounds of RAS, Moscow, Russia) Alexander Korlyukov (A.N. Nesmeyanov Institute of Organoelement Compounds of RAS, Moscow, Russia) Anna Vologzhanina (A.N. Nesmeyanov Institute of Organoelement Compounds of RAS, Moscow, Russia) Ekaterina Zorina-Tikhonova (Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow, Russia) Aleksandr Chistyakov (Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow, Russia) Aleksei Sidorov (Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow, Russia) Igor Eremenko (A.N. Nesmeyanov Institute of Organoelement Compounds of RAS, Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow, Russia)email: alex.d.volodin@gmail.comRecently some of us demonstrated that a number of zinc(II) malonates containing 1,2-bis(pyridin-4-yl)ethylene undergo a photoinitiated [2+2] cycloaddition reaction in a single-crystal-to-single-crystal manner [1]. Here, we present the results of our study of a novel photo-sensitive zinc(II) coordination complex containing two unsaturated fragments, namely, 1,2-bis(pyridin-4-yl)ethylene (bpe) and 2-allylmalonate (2-Amal). This complex was obtained from aqueous solution of zinc(II) acetate, 2-allylmalonic acid (H2Amal) and 1,2-bis(pyridin-4-yl)ethylene (bpe). Ethylene fragments of 2-allylmalonate and bpe are in the reactive positions (Figure, top). At irradiation for 8 hours the complex underwent [2+2] cycloaddition in a single-crystal-to-single-crystal manner to form a 2-((2,3-di(pyridin-4-yl)cyclobutyl)methyl)malonate (Figure, bottom). As both compounds are 3D coordination polymers, the process is the 3D → 3D reaction. The conversion rate was 50% in respect to 2-Amal. Further irradiation was accompanied by destruction of the single crystal and formation of an insoluble reaction product.
 
Figure. Fragment of molecular packing of [Zn2(H2O)2(2-Amal)2(bpe)] (top), and its photoreaction product (bottom).

This work was supported by the Russian Science Foundation (grant No. 17-13-01442) and the Russian Foundation for Basic Research (grant No. 16-33-60179).
 
References:

[1] E.N.Zorina-Tikhonova, A.S.Chistyakov, M.A.Kiskin, A.S.Sidorov, P.V.Dorovatovskii, Ya.V.Zubavichus, E.D.Voronova, I.A.Godovikov, A.A.Korlyukov, I.L.Eremenko, A.V.Vologzhanina (2018). IUCrJ 5, in press. DOI: https://doi.org/10.1107/S2052252518001641.
Keywords: solid-state reaction, [2+2] cycloaddition, photoinitiated reaction