Structure and Thermodynamic and Kinetic Properties of Eosin-Bipyridinium Complexes

Itamar Willner*, Yoav Eichen, Mordecai Rabinovitz, Roy Hoffman, Shmuel Cohen

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

44 Scopus citations

Abstract

Eosin, Eo2−, and N,N′-dimethyl-4,4′-bipyridinium, MV2+, form a crystalline 1:1 complex [Eo2−-MV2+]. With N,N′-dibenzyl-4,4′-bipyridinium, BV2+, the dye Eo2− forms a crystalline complex where one BV2+ unit is intercalated between two Eo2− units and the second BV2+ unit is positioned outside this sandwich structure [Eo2−-BV2+-Eo2−;BV2+]. Electrostatic, charge-transfer, and interactions stabilize these intermolecular assemblies. In solution, Eo2− and MV2+ initially form the 1:1 intermolecular structure [Eo2−-MV2+]. The latter complex is transformed to the thermodynamically stable complex structure [Eo2−-MV2+-Eo2−-MV2+] (in DMF, k = 57.3 M−1 s−1 at 331 K and Ea = 25.3 ± 0.5 kcal mol−1). The 1:1 complex [Eo2−-MV2+] shows thermal population of the charge-transfer band.

Original languageEnglish
Pages (from-to)637-644
Number of pages8
JournalJournal of the American Chemical Society
Volume114
Issue number2
DOIs
StatePublished - 1 Jan 1992

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