Electronic Structure and Triplet–Triplet Energy Transfer in Artificial Photosynthetic Antennas
Electronic Structure and Triplet–Triplet Energy Transfer in Artificial Photosynthetic Antennas
复制标题
人工光合天线中的电子结构和三重态-三重态能量转移
DOI：
10.1111/php.12979
复制
发表时间：
2018
影响因子：
3.3
通讯作者：
A. Moore
中科院分区：
文献类型：
--
作者：
Marely E. Tejeda;C. Brown;Gabriela C C C Coutinho;Ghabriel A Gomes de Sá;Julio L. Palma;Manuel J. Llansola‐Portoles;G. Kodis;V. Mujica;Junming Ho;D. Gust;T. Moore;A. Moore
制备了三种具有通过酰胺键连接的发色团的Pd（II）酞菁-类胡萝卜素二联体，以研究从四吡咯到共价连接的类胡萝卜素的三重态-三重态（T-T）能量转移速率作为类胡萝卜素中共轭双键数目的函数。研究了具有9、10和11个共轭双键的类胡萝卜素。瞬态吸收测量表明，在每种情况下，在Pd（II）酞菁中的系统间交叉发生在10 ps内，并且在带有9、10和11个双键的类胡萝卜素的二联体中，T-T能量转移分别发生在126、81和132 ps内。为了确定T-T能量转移速率的这种变化的起源，使用密度泛函理论（DFT）来计算三个二联体中的T-T电子耦合。根据计算，观察到的T-T能量转移趋势的主要原因是四吡咯和10-双键类胡萝卜素之间较大的T-T电子耦合。在9和11-双键类胡萝卜素中，与连接Pd（II）酞菁和类胡萝卜素的酰胺连接基相邻的甲基在10-双键类胡萝卜素中不存在，并且这种差异改变了其电子结构以增加偶联。
Three Pd(II) phthalocyanine–carotenoid dyads featuring chromophores linked by amide bonds were prepared in order to investigate the rate of triplet–triplet (T‐T) energy transfer from the tetrapyrrole to the covalently attached carotenoid as a function of the number of conjugated double bonds in the carotenoid. Carotenoids having 9, 10 and 11 conjugated double bonds were studied. Transient absorption measurements show that intersystem crossing in the Pd(II) phthalocyanine takes place in 10 ps in each case and that T‐T energy transfer occurs in 126, 81 and 132 ps in the dyads bearing 9, 10 and 11 double bond carotenoids, respectively. To identify the origin of this variation in T‐T energy transfer rates, density functional theory (DFT) was used to calculate the T‐T electronic coupling in the three dyads. According to the calculations, the primary reason for the observed T‐T energy transfer trend is larger T‐T electronic coupling between the tetrapyrrole and the 10‐double bond carotenoid. A methyl group adjacent to the amide linker that connects the Pd(II) phthalocyanine and the carotenoid in the 9 and 11‐double bond carotenoids is absent in the 10‐double bond carotenoid, and this difference alters its electronic structure to increase the coupling.
影响因子：
18.3
作者：
Polivka, Tomas;Frank, Harry A.
通讯作者：
Frank, Harry A.