Wavelength-dependent electron and energy transfer pathways in a side-to-face ruthenium porphyrin/perylene bisimide assembly

被引:176
作者
Prodi, A
Chiorboli, C
Scandola, F
Iengo, E
Alessio, E
Dobrawa, R
Würthner, F
机构
[1] Univ Ferrara, Dipartmento Chim, I-44100 Ferrara, Italy
[2] CNR, ISOF, Sez Ferrara, I-44100 Ferrara, Italy
[3] INSTM, Sez Ferrara, I-44100 Ferrara, Italy
[4] Univ Trieste, Dipartimento Sci Chim, I-34127 Trieste, Italy
[5] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany
关键词
D O I
10.1021/ja045379u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A new side-to-face supramolecular array of chromophores, where a pyridyl-substituted perylene bisimide dye axially binds to two ruthenium porphyrin fragments, has been prepared by self-assembly. The array is formulated as DPyPBI[Ru(TPP)(CO)](2), where DPyPBI = N,N'-di(4-pyridyl)-1,6,7,12-tetra(4tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide and TPP = 5,10,15,20-tetraphenylporphyrin. The photophysical behavior of DPyPBI[Ru(TPP)(CO)](2) has been studied by fast (nanoseconds) and ultrafast (femtoseconds) time-resolved techniques. The observed behavior sharply changes with excitation wavelength, depending on whether the DPyPBI or Ru(TPP)(CO) units are excited. After DPyPBI excitation, the strong fluorescence typical of this unit is completely quenched, and time-resolved spectroscopy reveals the occurrence of photoinduced electron transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 5.6 ps) followed by charge recombination (tau = 270 ps). Upon excitation of the Ru(TPP)(CO) fragments, on the other hand, ultrafast (tau < 1 ps) intersystem crossing is followed by triplet energy transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 720 ps). The perylene-based triplet state decays to the ground state on a longer time scale (tau = 9.8 mus). The photophysics of this supramolecular array provides remarkable examples of (i) wavelength-dependent behavior (a small change in excitation wavelength causes a sharp switch from electron to energy transfer) and (ii) intramolecular sensitization (the triplet state of the perylene bisimide, inaccessible in the free dye, is efficiently populated in the array).
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页码:1454 / 1462
页数:9
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