Time-Resolved Resonance Raman Spectroscopy of Metalloporphyrins in Excited Electronic States

激发电子态金属卟啉的时间分辨共振拉曼光谱

• 批准号: 9530707
• 负责人: Julio de Paula
• 金额: $ 13.26万
• 依托单位: Haverford College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-08-01 至 1999-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9530707&HistoricalAwards=false
• 关键词: Time; Resolved; Resonance; Raman; Spectroscopy

Julio C. de Paula of Haverford College is supported by the Experimental Physical Chemistry Program to investigate the nature of excited states of metalloporphyrins using time-resolved resonance Raman spectroscopy. The focus of his studies will be (a) to investigate equilibrium dynamics between conformers of tetraphenylporphyrins in triplet excited states, (b) to distinguish between charge-transfer and metal-centered excited states by varying the substituents on ruthenium and nickel ion complexes, and (c) to assign the time-resolved resonance Raman spectra of the cupric tetraphenylporphyrins. Metalloporphyrins have a rich photochemistry that may be applied to artificial photosynthesis, molecular electronics, and photodynamic cancer therapy. For example, free-base zinc and cupric porphyrins are known to sensitize tumor necrosis in vitro. Further, polymers of ruthenium porphyrins are photoconductive and can act as molecular wires. Non-planar metalloporphyrins are emerging as important compounds for a number of these applications, because distortions of the porphyrin ring modulate electrochemical and photochemical properties. These studies of the excited electronic states of metalloporphyrins will lead to a better understanding of their photochemical activity.

哈弗福德学院的Julio C. de Paula在实验物理化学项目的支持下，利用时间分辨共振拉曼光谱研究了金属卟啉激发态的性质。他的研究重点将是(a)研究四苯基卟啉在三重态激发态的构象之间的平衡动力学，(b)通过改变钌和镍离子配合物上的取代基来区分电荷转移和金属中心激发态，以及(c)分配四苯基铜卟啉的时间分辨共振拉曼光谱。金属卟啉具有丰富的光化学性质，可应用于人工光合作用、分子电子学和光动力癌症治疗等领域。例如，已知游离基锌和铜卟啉在体外对肿瘤坏死敏感。此外，钌卟啉聚合物具有光导性，可以作为分子导线。由于卟啉环的畸变可调节其电化学和光化学性质，非平面金属卟啉正成为许多此类应用的重要化合物。这些对金属卟啉的激发态的研究将有助于更好地理解它们的光化学活性。