Lawrence D S, Whitten D G
Department of Chemistry, University of Rochester, NY 14627, USA.
Photochem Photobiol. 1996 Dec;64(6):923-35. doi: 10.1111/j.1751-1097.1996.tb01857.x.
A series of novel, unsymmetrically substituted metallo-phthalocyanines was synthesized, along with their symmetrically substituted analogs, and the effects of structure and metal substitution on their photophysical and photoredox properties were investigated. The macrocycles were synthesized using a mixed-condensation method followed by chromatographic separation of the resulting soluble products. They possess a catechol "active site" and three tert-butyl groups for enhanced solubility. The ground- and excited-state photophysical properties of the free-base, Zn(II) and Pd(II) macrocycles were measured and compared with their symmetrically substituted (tetra[tert-butyl]) analogs. The efficiency with which these macrocycles sensitize the formation of singlet oxygen was determined and discussed in the context of the excited-state photophysical properties. Several examples of photoinduced electron transfer reactions with one- and two-electron acceptors are demonstrated and discussed. These soluble molecules can be tuned to optimize their photochemical and redox properties by varying the central metal, axial ligands and other substituents, thereby providing a series of molecules for the investigation of photodynamic therapy and photoinduced electron transfer mechanisms.
合成了一系列新型的、不对称取代的金属酞菁及其对称取代的类似物，并研究了结构和金属取代对其光物理和光氧化还原性质的影响。通过混合缩合方法合成大环化合物，然后对所得可溶性产物进行色谱分离。它们具有一个儿茶酚“活性位点”和三个叔丁基以提高溶解性。测定了游离碱、Zn(II)和Pd(II)大环化合物的基态和激发态光物理性质，并与其对称取代的（四[叔丁基]）类似物进行了比较。在激发态光物理性质的背景下，确定并讨论了这些大环化合物敏化单线态氧形成的效率。展示并讨论了与单电子和双电子受体发生光诱导电子转移反应的几个例子。通过改变中心金属、轴向配体和其他取代基，可以对这些可溶性分子进行调节，以优化其光化学和氧化还原性质，从而提供一系列用于研究光动力疗法和光诱导电子转移机制的分子。
