设计和合成结构新颖的聚合物太阳能电池给体材料是有机电子学的热点研究领域.首先利用二噻吩取代的苯并二噻吩(DBDT)作为富电子结构单元,吡咯并吡咯二酮(DPP)作为缺电子单元构筑了一种新的聚合物太阳能电池电子给体材料(PDBDTDPP),然后以[6,6]-苯基-C61-丁酸甲酯(PC61BM)作为电子受体,借助密度泛函理论(DFT)方法结合不相干的Marcus-Hush电荷传输模型,系统研究了PC61BM-DBDTDPPn=1,2,3,∞体系的分子结构、电子性质、光吸收性质、电荷转移的内重组能和外重组能、激子结合能、电荷传输积分、给体-受体界面上激子分离和电荷复合速率等性质,并利用线性回归方法分析了聚合物重复单元与其光伏性质的关系.结果表明,该聚合物具有较好的平面结构,低的最高占据分子轨道(HOMO)能级,在紫外-可见区具有宽且强的光学吸收、较大的激子束缚能(1.365 e V),小的激子分离内重组能(0.152 e V)和电荷复合内重组能(0.314 e V).在给体-受体界面上,激子分离速率高达1.073×1014 s-1,而电荷复合速率仅为1.797×108 s-1.相比较而言,激子分离速率比电荷复合速率高约6个数量级,表明在给体-受体界面上,光生激子具有很高的分离效率.总之,研究证明PDBDTDPP是一个非常有前途的聚合物太阳能电池给体材料,值得实验上进一步合成及器件化研究.理论研究不仅有助于更深入理解有机化合物结构与其光学、电子性质之间的关系,还可以为合理设计聚合物太阳能电池给体材料提供有价值的参考.
A new coordination polymer,{[Ag2（bpp）2（H2O）2]·bpdc·3H2O}n,derived from the ligand biphenyl-4,4＇-dicarboxylic acid（H2bpdc）,has been obtained through a hydrothermal technique（bpp = l,3-bis（4-pyridyl）propane）.Its single-crystal structure has been characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.The single-crystal X-ray diffraction reveals that complex 1 consists of 1D infinite[Ag（bpp）（H2O）]n^（n＋）cationic chains,2D anionic layer constructed by bpdc anions and free water which provide charge compensation in the crystal structure.The 1D infinite[Ag（bpp）（H2O）]n^（n＋） cationic chains and 2D anionic layer are further stacked in-ABAB- fashion through intermolecular H-bonding to form a 3D sandwich-like framework.In addition,the luminescent property of complex 1 in the solid state at room temperature was investigated.
LU Jiu-FuSHI JuanZHENG NanGUO Xiao-HuaGE Hong-Guang
A novel 3D MCP,[Co;（μ;-OH）(btc)（bmip）];(1,H;btc=1,3,5-benzenetricarboxylate acid,bmip=1,3-bis（2-methylimidazolyl）propane),was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.MCP 1 features a 3D framework based on tetranuclear Co（Ⅱ）clusters where the four cobalt ions are coplanar,and shows an unusual binodal（3,10）-connected topology.Furthermore,the photocatalytic experiment result indicates the degradation ratios of rhodamine B（RhB）reach 78.2%when MCP 1 acts as catalyst.
