TY - JOUR
T1 - Structure and Thermodynamic and Kinetic Properties of Eosin-Bipyridinium Complexes
AU - Willner, Itamar
AU - Eichen, Yoav
AU - Rabinovitz, Mordecai
AU - Hoffman, Roy
AU - Cohen, Shmuel
PY - 1992/1/1
Y1 - 1992/1/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0001753912&partnerID=8YFLogxK
U2 - 10.1021/ja00028a033
DO - 10.1021/ja00028a033
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AN - SCOPUS:0001753912
SN - 0002-7863
VL - 114
SP - 637
EP - 644
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 2
ER -