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

5,15 二乙基 10,20 二苯基的激发态光谱

• 批准号: 6120167
• 负责人: M J THERIEN
• 金额: $ 0.91万
• 依托单位: UNIVERSITY OF PENNSYLVANIA
• 依托单位国家: 美国
• 资助国家: 美国
• 起止时间: 至
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/6120167
• 关键词: biological products; biomedical resource; informatics

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).)

[5，10，15，20-四苯基卟啉]铜（Ⅱ）的光激发 {CuTPP}通常伴随着非常有效的系统间 单双峰与三双峰的交叉（< 10 ps）， 通过与顺磁d9相互作用的trip-四重流形 铜中心。 相关化合物的瞬态共振拉曼研究进展 [5，15-双[（4 '-硝基苯基）乙炔基]-10，20-二苯基卟啉] - 铜（II）{I}和电子不对称的 [5-[[4 '-（二甲氨基）苯基]乙炔基] -15-[（4”-硝基苯基）乙炔基]-10，20-二苯基卟啉合]-铜（II） {II}显示激发态光谱与大量电子 转移（ET）从卟啉大环到硝基部分， 通过N-O伸缩频率的20 cm-1下移显示。 与30 mW激光功率瞬态共振拉曼光谱不同， CuTPP显示出与激发和接地一致的特征 状态贡献，光谱的I和II显示没有检测到 即使在4%的激光功率下检查时， 用于CuTPP实验。 观察到的漂白 I和II中的基态与相对长寿命的 激发态 为了阐明这些分子的激发态动力学 化合物，我们建议进行三重态-三重态瞬态吸收 以及I和II的磷光寿命测量， 未取代的化合物， [5，15-双[（苯基）乙炔基]-10，20-二苯基卟啉合]铜（II），作为 以及这三种化合物的锌类似物。 （这些结果 已发表在J. Amer. Chem. Soc. 119，12578（1997）中。