Charge-transfer complexes of benzylviologen (1,1′-dibenzyl-4,4′-bipyridinium(2+) cation) with cyanocuprate(I) and the structure of (BzV)<inf>3</inf>Cu<inf>9</inf>(CN)<inf>15</inf>·H<inf>2</inf>O

Michiko B. Inoue, Motomichi Inoue, Lorena Machi, Francisco Brown, Quintos Fernando

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Abstract

Reactions between 1,1′-dibenzyl-4,4′-bipyridinium(2+) (benzylviologen, BzV) chloride and cyanocuprates(I) gave two charge-transfer complexes having different colors: dark brown (BzV)3Cu9(CN)15·H2O and light brown (BzV)Cu(CN)3·2H2O. An X-ray crystal analysis of the former compound showed that nine crystallographically nonequivalent Cu atoms form three kinds of triad Cu(CN)Cu screws, which are linked by CN groups resulting in a unique three-dimensional network structure. Three of the nine Cu atoms have distorted tetrahedral (td) coordination geometries while the others have triangular plane (tp) geometries. Each screw consists of a (-tp-td-tp-)narray. There are three crystallographically nonequivalent viologen molecules. Certain CuCN moieties are located above a viologen ring or by the side of a viologen ring, with close interatomic contacts. These close contacts are characteristic of the charge-transfer complex and are responsible for the deep color of the complex. © 1995.
Original languageAmerican English
Pages (from-to)145-151
Number of pages7
JournalInorganica Chimica Acta
DOIs
StatePublished - 1 Mar 1995

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