Highly coupled dyads based on phthalocyanine-ruthenium(II) tris(bipyridine) complexes.: Synthesis and photoinduced processes

被引:47
作者
González-Cabello, A
Vázquez, P
Torres, T
Guldi, DM [1 ]
机构
[1] Univ Autonoma Madrid, Fac Ciencias, Dept Quim Organ C I, E-28049 Madrid, Spain
[2] Univ Notre Dame, Radiat Lab, Notre Dame, IN 46556 USA
关键词
D O I
10.1021/jo0341968
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A new series of multicomponent ZnPc-Ru(bpy)(3) Systems, 1a-c, consisting of a zinc-phthalocyanine linked through conjugated and/or nonconjugated connections to a ruthenium(II) tris(bipyridine) complex, has been synthesized. The ruthenium complexes la-c were prepared from phthalocyanines 2a-c, bearing a 4-substituted-2,2'-bipyridine ligand by treatment with [Ru(bpy)(2)Cl-2](.)2H(2)O. Different synthetic strategies have been devised to prepare the corresponding dyad precursors (2a-c). Compound 2a, for example, with an ethenyl bridge, was synthesized by statistical condensation of 4-tert-butylphthalonitrile and 5-[(E)-2-(3,4-dicyanophenyl)ethenyl]-2,2'-bipyridine (3) in the presence of zinc chloride. Compounds 2b and 2c, having, respectively, an amide or an ethynyl bridge, were prepared following a different synthetic approach. The method involves the coupling of an appropriate 5-substituted-2,2'-bipyridine to an unsymmetrical phthalocyanine suitably functionalized with an amino (4) or an ethynyl group (5). The photophysical properties of the dyads that are ZnPe-Ru(bpy)(3) 1a-c and related model compounds have been determined by a variety of steady-state (i.e., fluorescence) and time-resolved methods (i.e., fluorescence and transient absorption). Clearly, intramolecular electronic interactions between the two subunits dominate the photophysical events following the initial excitation of either chromophore. These intramolecular interactions lead, in the case of photoexcited ZnPc, to faster intersystem crossing kinetics compared to a ZnPc reference, while photoexcited [Ru(bpy)(3)](2+) Undergoes a rapid and efficient transduction of triplet excited-state energy to the Pc.
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页码:8635 / 8642
页数:8
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