Exploitation of knowledge databases in the synthesis of zinc(II) malonates with photo-sensitive and photo-insensitive N,N′-containing linkers

IUCrJ

Kiskin, M.A.¹  Zorina-Tikhonova, E.N.²  Chistyakov, A.S.³  Sidorov, A.A.⁴ 

[1] A. N. Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, 119991, Russian Federation;N. S. Kurnakov Institute of General and Inorganic Chemistry RAS, Leninskii Pr., 31, Moscow, 119991, Russian Federation;National Research Center Kurchatov Institute, Ploshchad' Akademika Kurchatova, 1, Moscow, 123098, Russian Federation;Pirogov Russian National Research Medical University, Ostrovityanov Street, 1, Moscow, 117997, Russian Federation

关键词: CRYSTAL ENGINEERING;    CRYSTAL STRUCTURE PREDICTIONS;    COORDINATION POLYMERS;    ORGANIC SOLID-STATE REACTIONS;    CYCLOADDITION REACTIONS;    SINGLE-CRYSTAL-TO-SINGLE-CRYSTAL TRANSFORMATIONS;    PHOTO-SENSITIVE LIGANDS;   

DOI  :  10.1107/S2052252518001641

学科分类：数学（综合）

来源: International Union of Crystallography

【 摘 要 】

Photoinitiated solid-state reactions are known to affect the physical properties of coordination polymers, such as fluorescence and sorption behaviour, and also afford extraordinary architectures (e.g. three-periodic structures with polyorganic ligands). However, the construction of novel photo-sensitive coordination polymers requires an understanding of the factors which govern the mutual disposition of reactive fragments. A series of zinc(II) malonate complexes with 1,2-bis(pyridin-4-yl)ethylene and its photo-insensitive analogues has been synthesized for the purpose of systematic analysis of their underlying nets and mutual disposition of N-donor ligands. The application of a big data-set analysis for the prediction of a variety of possible complex compositions, coordination environments and networks for a four-component system has been demonstrated for the first time. Seven of the nine compounds possess one of the highly probable topologies for their underlying nets; in addition, two novel closely related four-coordinated networks were obtained. Complexes containing 1,2-bis(pyridin-4-yl)ethylene and 1,2-bis(pyridin-4-yl)ethane form isoreticular compounds more readily than those with 4,4′-bipyridine and 1,2-bis(pyridin-4-yl)ethylene. The effects of the precursor, either zinc(II) nitrate or zinc(II) acetate, on the composition and dimensionality of the resulting architecture are discussed. For three of the four novel complexes containing 1,2-bis(pyridin-4-yl)ethylene, the single-crystal-to-single-crystal [2 + 2] cycloaddition reactions were carried out. UV irradiation of these crystals afforded either the 0D→1D or the 3D→3D transformations, with and without network changes. One of the two 3D→3D transformations was accompanied by solvent (H2O) cleavage.

【 授权许可】

CC BY