Ricciardi Giampaolo, Soldatova Alexandra V, Rosa Angela
Dipartimento di Chimica, Università della Basilicata, Via N. Sauro 85, 85100 Potenza, Italy.
J Inorg Biochem. 2008 Mar;102(3):406-13. doi: 10.1016/j.jinorgbio.2007.10.029. Epub 2007 Nov 28.
A comprehensive understanding of the factors governing the efficiency of metallophthalocyanine-based photothermal sensitizers requires the knowledge of their excited-state dynamics. This can only be properly gained when the nature and energy of the excited states (often spectroscopically silent) lying between the photogenerated state and the ground state are known. Here the excited state deactivation mechanism of two very promising metallophthalocyanine-based photothermal sensitizers, NiPc(OBu)(8) and NiNc(OBu)(8), is reviewed. It is shown that time dependent density functional theory (TDDFT) methods are capable to provide reliable information on the nature and energies of the low-lying excited states along the relaxation pathways. TDDFT calculations and ultrafast experiments consistently show that benzoannulation of the Pc ring modifies the photodeactivation mechanism of the photogenerated S(1)(pi,pi*) state by inducing substantial changes in the relative energies of the excited states lying between the S(1)(pi,pi*) state and the ground state.
要全面理解影响金属酞菁基光热敏化剂效率的因素，需要了解其激发态动力学。只有当知道光生态和基态之间的激发态（通常在光谱上无特征）的性质和能量时，才能正确获得这方面的知识。本文综述了两种非常有前景的金属酞菁基光热敏化剂NiPc(OBu)(8)和NiNc(OBu)(8)的激发态失活机制。结果表明，含时密度泛函理论（TDDFT）方法能够提供沿弛豫路径的低激发态的性质和能量的可靠信息。TDDFT计算和超快实验一致表明，酞菁环的苯并环化通过引起S(1)(π,π*)态和基态之间激发态相对能量的显著变化，改变了光生S(1)(π,π*)态的光失活机制。
