Linearly extended π-conjugated dithiafulvene polymer formed soluble charge-transfer complex with 7,7,8,8-tetracyanoquinodimethane
Linearly extended π-conjugated dithiafulvene polymer formed soluble charge-transfer complex with 7,7,8,8-tetracyanoquinodimethane
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DOI：
10.1295/polymj.32.435
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发表时间：
2000-01-01
期刊：
影响因子：
2.8
通讯作者：
Chujo, Y
中科院分区：
文献类型：
--
作者：
Naka, K;Uemura, T;Chujo, Y
当将7,7,8,8-四氰喹啉二甲烷（TCNQ）加入到二甲基亚砜（DMSO）溶液中时，π共轭给体聚合物与TCNQ形成了可溶性电荷转移（CT）配合物(2)。在DMSO中，2与TCNQ反应生成深绿色溶液。将沉淀的TCNQ过滤后，蒸发滤液，得到墨绿色粉末。所得CT配合物可溶于乙腈、DMSO、N，N-二甲基甲酰胺（DMF）、丙酮和甲醇，部分可溶于四氢呋喃（THF）。紫外-可见吸收光谱表明，形成的CT配合物含有约1:1的比例的二硫脲单位与TCNQ。紫外-可见吸收和FT-IR分析表明，TCNQ加入到2的溶液中时，其阴离子自由基最初是通过电荷转移反应形成的，剩余的TCNQ以部分电荷转移形式与2相互作用。在H-1核磁共振光谱中，归属于2的苄基质子的宽峰被转移到与TCNQ进料比成比例的较低磁场中，而不是二硫代磺烯单位2。CT配合物的电导率为2 × 10(-4) S cm(-1)，比未配合的聚合物高3个数量级。
A soluble charge-transfer (CT) complex of pi-conjugated donor polymer with 7,7,8,8-tetracyanoquinodimethane (TCNQ) was formed when TCNQ was added to a dimethyl sulfoxide (DMSO) solution of a pi-conjugated poly(dithiafulvene) (2). In DMSO, 2 reacted with TCNQ to produce a dark green solution. After the precipitated TCNQ was filtered, the filtrate was evaporated to obtain a dark green powder. The resulting CT complex was soluble in acetonitrile, DMSO, N,N-dimethylformamide (DMF), acetone, and MeOH, and partially soluble in tetrahydrofuran (THF). The UV-Vis absorption spectra suggested a formation of the CT complex containing about 1 : 1 ratio of dithiafulvene unit to TCNQ. The UV-Vis absorption and FT-IR analyses indicated that the anion radical of TCNQ was initially formed by the charge-transfer reaction when TCNQ was added to the solution of 2, and the remaining TCNQ was interacted with 2 as a partially charge-transferred form. In the H-1 NMR spectra, the broad peak attributed to the benzylidene proton of 2 was shifted to a lower magnetic field proportional to the TCNQ feed ratio against the dithiafulvene unit of 2. The CT complex has a conductivity of 2 x 10(-4) S cm(-1), three orders of magnitude greater than the uncomplexed polymer.