Synthesis, transient absorption, and transient resonance Raman spectroscopy of novel electron donor-acceptor complexes:: [5,15-bis[(4′-nitrophenyl)ethynyl]-10,20-diphenylporphinato]copper(II) and [5-[[4′-(dimethylamino)phenyl]ethynyl]-15-[(4"-nitrophenyl)ethynyl]-10,20-diphenyl-porphinato]copper(II)

被引:60
作者
LeCours, SM
Philips, CM
de Paula, JC
Therien, MJ
机构
[1] Haverford Coll, Dept Chem, Haverford, PA 19041 USA
[2] Univ Penn, Dept Chem, Philadelphia, PA 19104 USA
关键词
D O I
10.1021/ja964436j
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report the synthesis, transient absorption, FT Raman, resonance Raman, time-resolved resonance Raman, and transient resonance Raman spectra of pseudo-D-2h symmetric [5, 15-bis[(4'-nitrophenyl)ethynyl]-10, 20-diphenylporphinato]copper(II) (I) and electronically asymmetric [5-[4'-(dimethylamino)phenyl]ethynyl]-15-[(4 "-nitrophenyl)ethynyl]-10, 20-diphenylporphinato]copper(II) (II), which bears both electron-releasing and electron-withdrawing groups conjugated directly to the porphyrin periphery. The spectroscopic results suggest extensive electronic communication between the 5- and 15-arylethynyl groups and the porphyrin core. Relative to the parent compound, (tetraphenylporphinato)copper(II) (CuTPP), the arylethynyl substituents increase the lifetime of the excited trip-multiplet states, CuTPP, as well as compounds I and II, however, shows similar solvent-dependent dynamics: the trip-multiplet lifetimes are longer in a noncoordinating solvent such as benzene than in a coordinating solvent such as THF. This behavior is consistent with the existence of a quenching state whose effect is more pronounced upon coordination of solvent. The time-resolved resonance Raman spectrum of compound II shows features commonly associated with the relatively long-lived triplet excited states of copper(II) porphyrins. The transient resonance Raman spectrum of a short-lived excited state present in both compounds I and II is characterized by marked shifts in the nitro and porphyrin stretching frequencies relative to that observed for the ground stares of both (4-nitrophenyl)-ethyne and (tetraphenylporphinato)copper(II). We interpret these results for the compounds I and II as arising from (i) a short-lived excited state present at early time that possesses enhanced porphyrin-to-nitro charge-transfer character with respect to the ground state and (ii) a longer-lived excited state deriving from this initially probed charge-transfer state that is largely porphyrin localized.
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页码:12578 / 12589
页数:12
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