Department of Chemistry, Indian Institute of Technology, Bombay, Powai, Mumbai 400 076, India.
Inorg Chem. 2010 Mar 15;49(6):2692-700. doi: 10.1021/ic901920y.
The thiaporphyrin building blocks with N(3)S and N(2)S(2) cores containing one hydroxyphenyl functional group at the meso position were synthesized by adopting the unsymmetrical thiophene diol method. These monohydroxy thiaporphyrins were used to construct the first examples of axial bonding type Sn(IV) porphyrin triads in which Sn(IV) porphyrin acts as basal unit and the two thiaporphyrin units as axial ligands by treating with SnTTP(OH)(2) in benzene at refluxing temperature. The axial bonding type triads were confirmed by mass, 1D and 2D NMR studies. The absorption and electrochemical studies support weak ground state interaction among the porphyrin subunits within the porphyrin triads. The fluorescence studies indicate there is a possibility of energy transfer at the singlet state from basal Sn(IV) porphyrin unit to axial thiaporphyrin units.
采用非对称噻吩二醇法合成了具有 N(3)S 和 N(2)S(2)核且在中位含有一个羟苯基官能团的噻吩卟啉砌块。这些单羟基噻吩卟啉被用于构建首例轴向键合型 Sn(IV)卟啉三联体,其中 Sn(IV)卟啉作为基本单元,两个噻吩卟啉单元作为轴向配体,通过在回流温度下的苯中处理 SnTTP(OH)(2)来实现。轴向键合型三联体通过质量、1D 和 2D NMR 研究得到确认。吸收和电化学研究支持卟啉三联体中卟啉亚基之间的弱基态相互作用。荧光研究表明,从基底 Sn(IV)卟啉单元到轴向噻吩卟啉单元,在单重态可能存在能量转移。