EXCITE STATE SPECTRA OF 5,15 BISETHYNYL 10,20 DIPHENYL & 10,20 DIPHENYL COMPLEX

[5，10，15，20-四苯基卟啉]铜(II)的光激发 {CuTPP}通常伴随着非常高效的系统间 将二重唱(&lt；10ps)交叉到二重唱，并 通过与顺磁D9的相互作用实现的Trip-Quartet流形 铜质中心。 相关化合物的暂态共振拉曼光谱研究进展 [5，15-双[(4‘-硝基苯基)乙炔]-10，20-二苯基卟啉] -铜(II){I}和电子不对称 [5-[[4‘-(二甲氨基)苯基]乙炔] -15-[(4“-nitrophenyl)ethynyl]-10，20-diphenylporphinato]-copper(II) {II}揭示了与实质性电子一致的激发态谱 将(ET)从卟啉大环转移到硝基部分，如 显示为N-O伸展频率的20厘米-1下移。 与30 mW激光功率的暂态共振拉曼光谱不同 CuTPP，表现出与激发和接地一致的特征 态贡献时，I和II的光谱都没有检测到 基态贡献即使在激光功率的4%被检查时也是如此 在CuTPP实验中使用。观察到的漂白现象 在I和II中的基态与相对较长的 激动态。为了阐明这些分子的激发态动力学 化合物，我们建议进行三重-三重暂态吸收 和磷光寿命测量I和II以及 未取代化合物， [5，15-bis[(phenyl)ethynyl]-10，20-diphenylporphinato]copper(II)，AS 以及这三种化合物的锌类似物。(这些结果 已发表在《美国医学会杂志》上。化学。SoC。12578(1997年)。)

Photoexcitation of [5, 10, 15, 20-tetraphenylporphinato]copper(II) {CuTPP} is typically accompanied by very efficient intersystem crossing (< 10 ps) of the sing-doublet to the trip-doublet and trip-quartet manifold through interaction with the paramagnetic d9 copper center. Recent transient resonance Raman investigations of related compounds [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} reveal excited state spectra consistent with substantial electron transfer (ET) from the porphyrin macrocycle to the nitro moiety as displayed by 20 cm-1 downshifts of the N-O stretching frequency. Unlike the 30 mW laser power transient resonance Raman spectrum of CuTPP which shows features consistent with both excited and ground state contributions, the spectra of both I and II show no detectable ground state contributions even when examined at 4% of the laser power employed in the CuTPP experiment. The observed bleaching of the ground state in I and II is consistent with a relatively long-lived excited state. To elucidate the excited state dynamics of these compounds, we propose performing triplet-triplet transient absorption and phosphorescent lifetime measurements of I and II as well as the unsubstituted compound, [5,15-bis[(phenyl)ethynyl]-10,20-diphenylporphinato]copper(II), as well as the zinc analogs of these three compounds. (These results have been published in J. Amer. Chem. Soc. 119, 12578 (1997).)