Journal
CHEMPHYSCHEM
Volume 7, Issue 7, Pages 1514-1519Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.200600065
Keywords
energy transfer; photochemistry; porphyrinoids; supramolecular chemistry; time-resolved spectroscopy
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The molecular box 1 comprises of two zinc-porphyrin metallacycles connected by two free-base 4'-trans-dipyridylporphyrins, axially coordinated to the zinc centers. The photophysics of 1 were studied in chloroform by emission and ultrafast absorption spectroscopy. In the molecular box, fast singlet energy transfer (main component, tau = 32 ps) is observed to occur from zinc-porphyrin metallacycles to the free-base chromophores. From wave-length-dependent spectrofluorimetric data, the efficiency of the energy-transfer (ET) process is estimated as 0.5. The lower-than-unity value is tentatively attributed to the possibility of a competing electron-transfer quenching pathway. Molecular box 1 can be considered to be a simple, self-assembling, six-chromophore antenna system. It has an inner cavity, 11.4 angstrom wide, that could be used, in principle, to host a variety of guest molecules and obtain higher-order assemblies.
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