화학공학소재연구정보센터
Inorganic Chemistry, Vol.54, No.17, 8482-8494, 2015
Modulation of Energy Transfer into Sequential Electron Transfer upon Axial Coordination of Tetrathiafulvalene in an Aluminum(III) Porphyrin-Free-Base Porphyrin Dyad
Axially assembled aluminum(III) porphyrin based dyads and triads have been constructed to investigate the factors that govern the energy and electron transfer processes in a perpendicular direction to the porphyrin plane. In the aluminum(III) porphyrin-free-base porphyrin (AlPor-Ph-H(2)Por) dyad, the AlPor occupies the basal plane, while the free-base porphyrin (H(2)Por) with electron withdrawing groups resides in the axial position through a benzoate spacer. The NMR, UV-visible absorption, and steady-state fluorescence studies confirm that the coordination of pyridine appended tetrathiafulvalene (TTF) derivative (TTF-py or TTF-Ph-py) to the dyad in noncoordinating solvents afford vertically triads (TTF-py -> AlPor-Ph-H(2)Por and TTF-Ph-py -> AlPor-Ph-H(2)Por). Time-resolved studies revealed that the AlPor in dyad and triads undergoes photoinduced energy and/or electron transfer processes. Interestingly, the energy and electron donating/accepting nature of AlPor can be modulated by changing the solvent polarity or by stimulating a new competing process using a TTF molecule. In modest polar solvents (dichloromethane and nu-dichlorobenzene), excitation of AlPor leads singlet-singlet energy transfer from the excited singlet state of AlPor ((1)AlPor*) to H(2)Por with a moderate rate constant (k(EnT)) of 1.78 x 10(8) s(-1). In contrast, excitation of AlPor in the triad results in ultrafast electron transfer from TTF to (1)AlPor* with a rate constant (k(ET)) of 8.33 x 10(9)-1.25 x 10(10) s(-1), which outcompetes the energy transfer from (1)AlPor* to H(2)Por and yields the primary radical pair TTF+center dot-AlPor(-center dot)-H(2)Por. A subsequent electron shift to H(2)Por generates a spatially well-separated TTF+center dot-AlPor-H(2)Por(-center dot) radical pair.