Synthesis and properties of a twin donor molecule composed of cofacially stacked dihydrodiazapentacenes
Synthesis and properties of a twin donor molecule composed of cofacially stacked dihydrodiazapentacenes
复制标题
共面堆叠二氢二氮杂五苯双供体分子的合成与性质
DOI：
10.1039/c7qm00563f
复制
发表时间：
2018
影响因子：
7
通讯作者：
S. Seki
中科院分区：
文献类型：
--
作者：
D. Sakamaki;H. Saeki;S. Seki
以6，13-二氢-6，13-二氮并五苯（DHDAP）为构筑单元，合成了一种夹形的给体-受体-给体（D-A-D）分子（1）。X-射线单晶分析揭示了1的结构，其DHDAP部分彼此紧邻。电化学测量表明，该分子可被氧化至四价化，反映了其具有两个DHDAP单元的孪生给体结构。光谱测量（UV/可见-NIR，ESR）的1 stec+建议的自由基自旋的两个DHDAP单位的充分离域。稳定的自由基阳离子盐1 stec+·[SbF 6]−通过1的化学氧化得到。1 stec+·[SbF 6]−的堆积结构是一种偏聚堆积，这是电荷传导所需要的。实际上，通过微波技术的光电导测量显示，1 stec+·[SbF 6]−的光电导比其中性态高10倍以上，具有非常长的电荷分离态寿命，这表明其即使在近红外区域也可以作为光能收集核心。
A clip-shaped donor–acceptor–donor (D–A–D) molecule (1) has been prepared with 6,13-dihydro-6,13-diazapentacene (DHDAP) as a building unit. X-Ray single crystal analysis revealed the structure of 1 whose DHDAP moieties confront each other in close proximity. The electrochemical measurements showed that this molecule could be oxidized up to the tetracation reflecting its twin donor structure with two DHDAP units. Spectroscopic measurements (UV/vis-NIR, ESR) of 1˙+ suggested the full delocalization of the radical spin over the two DHDAP units. The stable radical cation salt 1˙+·[SbF6]− was obtained by chemical oxidation of 1. The packing structure of 1˙+·[SbF6]− was a kind of segregated stacking, which is desirable for charge conduction. Actually, photoconductivity measurement by the microwave technique revealed that 1˙+·[SbF6]− has more than 10 times higher photoconductivity than its neutral state with an extraordinary long lifetime of charge separated states, suggesting its feasibility as light-energy harvesting cores even in the near-IR region.