Hydrogen bonds not only provide a structural scaffold to assemble donor and acceptor moieties of zinc porphyrin-quinone dyads but also control the photoinduced electron transfer to afford the long-lived charge-separated states.
Hydrogen bonds not only provide a structural scaffold to assemble donor and acceptor moieties of zinc porphyrin-quinone dyads but also control the photoinduced electron transfer to afford the long-lived charge-separated states.
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DOI：
10.1021/jp050352y
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发表时间：
2005-04
期刊：
影响因子：
--
通讯作者：
K. Okamoto;S. Fukuzumi
中科院分区：
文献类型：
--
作者：
K. Okamoto;S. Fukuzumi
设计并合成了一系列锌卟啉-醌连接的二元体[ZnP-CONH-Q、ZnP-NHCO-Q和ZnP-n-Q (n = 3、6、10)]来研究氢键的影响，氢键不仅可以提供组装供体和受体部分的结构支架，还可以控制光诱导电子转移过程。对于 ZnP-CONH-Q 和 ZnP-NHCO-Q，N-H 质子与 Q 的羰基氧之间的氢键导致 Q 的还原电位发生变化。ZnP-CONH-Q*-、ZnP-NHCO-Q*- 和 ZnP-n-Q*- (n = 3, 6, 10) 中 N-H 质子与 Q*- 的羰基氧之间的强氢键由ESR 谱证实了化学还原，其表现出的超精细耦合常数与密度泛函计算预测的一致。另一方面，对于 ZnP-n-Q (n = 3, 6, 10)，两个酰胺基之间的氢键提供了一个结构支架，将供体 (ZnP) 和受体 (Q) 部分与 N-H 质子和 Q 的羰基氧之间的氢键组装在一起，从而实现电荷分离状态，寿命长达微秒。
A series of zinc porphyrin-quinone linked dyads [ZnP-CONH-Q, ZnP-NHCO-Q, and ZnP-n-Q (n = 3, 6, 10)] were designed and synthesized to investigate the effects of hydrogen bonds which can not only provide a structural scaffold to assemble donor and acceptor moieties but also control the photoinduced electron-transfer process. In the case of ZnP-CONH-Q and ZnP-NHCO-Q, the hydrogen bond between the N-H proton and the carbonyl oxygen of Q results in the change in the reduction potential of Q. The strong hydrogen bond between the N-H proton and the carbonyl oxygen of Q*- in ZnP-CONH-Q*-,ZnP-NHCO-Q*-, and ZnP-n-Q*- (n = 3, 6, 10) generated by the chemical reduction has been confirmed by the ESR spectra, which exhibit hyperfine coupling constants in agreement those predicted by the density functional calculations. In the case of ZnP-n-Q (n = 3, 6, 10), on the other hand, the hydrogen bond between two amide groups provides a structural scaffold to assemble the donor (ZnP) and the acceptor (Q) moiety together with the hydrogen bond between the N-H proton and the carbonyl oxygen of Q, leading to attainment of the charge-separated state with a long lifetime up to a microsecond.