Instituto de Nanociencia Nanotecnología y Materiales Moleculares (INAMOL), Universidad de Castilla-La Mancha, 45071-Toledo, Spain.
Phys Chem Chem Phys. 2014 Feb 14;16(6):2443-51. doi: 10.1039/c3cp54280g.
Two novel donor-bridge-acceptor arrays (ZnP-nTV-C60) with zinc porphyrin (ZnP) and fullerene (C60), covalently connected by oligo(thienylenevinylene) (nTV) molecular wires (n = 3 and 8; ), have been prepared in a multistep convergent manner. The influence of the nTV-length on the electrochemical and electronic properties of the ZnP-nTV-C60 triads has been revealed. Interestingly, an efficient photoinduced electron transfer process occurs in both triads with formation of intermediate radical-ion pairs (namely, ZnP˙(+)-nTV-C60˙(-) and ZnP-nTV˙(+)-C60˙(-)) as confirmed by the nanosecond transient absorption measurements in the visible and NIR regions. In polar and nonpolar solvents, the rate constants of charge-separation processes (kCS) via(1)ZnP*-nTV-C60 were found to decrease from ca. 1.2 × 10(10) s(-1) for n = 3 (RDA = 20 Å) to (5-7) × 10(9) s(-1) for n = 8 (RDA = 60 Å) on the basis of fluorescence lifetime measurements of the ZnP moiety. From these data, together with those previously obtained ones for n = 4 in the related ZnP-nTV-C60 systems, a low attenuation coefficient was evaluated for the nTV molecular wires.
两个新型给体-桥-受体（ZnP-nTV-C60）阵列，具有锌卟啉（ZnP）和富勒烯（C60），通过寡聚（噻吩亚乙烯基）（nTV）分子线（n = 3 和 8）共价连接，采用多步收敛方式制备。研究了 nTV 长度对 ZnP-nTV-C60 三联体的电化学和电子性质的影响。有趣的是，在两个三联体中都发生了有效的光诱导电子转移过程，形成了中间自由基离子对（即，ZnP˙(+)-nTV-C60˙(-)和 ZnP-nTV˙(+)-C60˙(-)），这通过在可见和近红外区域的纳秒瞬态吸收测量得到证实。在极性和非极性溶剂中，通过（1）ZnP*-nTV-C60 的电荷分离过程（kCS）的速率常数，基于 ZnP 部分的荧光寿命测量，从 n = 3（RDA = 20 Å）的约 1.2×10(10) s(-1)减小到 n = 8（RDA = 60 Å）的（5-7）×10(9) s(-1)。根据这些数据，以及之前在相关 ZnP-nTV-C60 系统中获得的 n = 4 的数据，评估了 nTV 分子线的低衰减系数。
