Synthesis of bis-porphyrins containing a 2,9-diphenyl-1,10-phenanthroline spacer
作者:Sylvie Chabdon-Noblat、Jean-Pierre Sauvage
DOI:10.1016/s0040-4020(01)87125-8
日期:1991.1
10-phenanthroline spacer. Two routes have been investigated: a stepwise procedure and a direct strategy involving a double cyclisation step. From the bis-free base porphyrin, synthesized with an overall yield of ∼1% from 2,9-di(p-tolyl)-1,10-phenanthroline, an unsymmetrical zinc (II) porphyrin free base system was prepared and isolated in view of excited state energy and electron transfer.
A new [2]catenane containing four Rh(III) porphyrins has been prepared following a three-step strategy: (i) Cu(I)-driven entwining of two free base porphyrin-bearing bidentate chelates, followed by (ii) insertion of rhodium in the porphyrin nuclei, and finally (iii) cyclisation via the formation of N–Rh coordination bonds. Direct metalation of porphyrinic compounds with [Rh(CO)2Cl]2 was not met with
作者:Chardon-Noblat, Sylvie、Sauvage, Jean-Pierre、Mathis, Paul
DOI:——
日期:——
Photophysics of entwined porphyrin conjugates: competitive exciton annihilation, energy-transfer, electron-transfer, and superexchange processes
作者:Anne M. Brun、Stephen J. Atherton、Anthony Harriman、Valerie Heitz、Jean Pierre Sauvage
DOI:10.1021/ja00038a028
日期:1992.6
Bisgold(III) bisporphyrins, in which a 1,10-phenanthroline spacer imposes a constrained geometry, have been synthesized. Flash photolysis studies indicate that, at high laser intensity, triplet exciton annihilation occurs with a diffusion coefficient of 4 x 10(-5) cm2 s-1. Two such molecules coordinate to a copper(I) ion, via the 1, 10-phenanthroline spacers, to form a tetrameric porphyrin ensemble in which triplet exciton annihilation competes with electron transfer from the copper(I) complex to a gold porphyrin triplet. A mixed multicomponent array, comprising gold(III) and zinc(II) bisporphyrins covalently-linked to a copper(I) bis(1,10-phenanthroline) complex, undergoes a variety of electron-transfer reactions according to which porphyrin absorbs the photon energy. The copper(I) complex participates in these electron-transfer processes via both direct (redox) and indirect (superexchange) mechanisms.