Heteroleptic Copper Dipyrromethene Complexes: Synthesis, Structure, and Coordination Polymers

The synthesis of neutral [Cu(dpm)2] and [Cu(dpm)(acac)] (dpm = dipyrromethene, acac = acetylacetonato) complexes
is presented. The formation of the asymmetric metal complexes was monitored by electronic absorption and infrared
spectroscopy. Two of the complexes investigated, containing pyrdpm ligands (pyrdpm = pyridyldipyrromethene),
form 1-dimensional coordination polymers. The coordination polymers formed by these complexes have been
characterized by single-crystal X-ray diffraction, differential scanning calorimetry, and thermogravimetric analysis.
The complexes possess square pyramidal coordination geometries with the apical position occupied by the meso-pyridyl donor of a neighboring complex in the crystal lattice. The features of these coordination complexes that
facilitate formation of extended solids have been probed. Symmetric [Cu(pyrdpm)2] complexes are unable to form
coordination solids due to steric hindrance at the metal center. Use of cyano donors in complexes such as
[Cu(cydpm)(acac)] (cydpm = cyanodipyrromethene) in lieu of pyridyl donors also fail to form network solids. Through
these systematic studies, both the basic coordination chemistry of these complexes and the fundamental design
requirements for synthesizing this novel class of coordination polymers have been defined.

本论文阐述了中性[Cu(dpm)2]和[Cu(dpm)(acac)]（dpm = 二吡咯甲烷，acac = 乙酰丙酮酸）配合物的合成过程。通过电子吸收光谱和红外光谱对非对称金属配合物的形成进行了监测。研究中，含有吡啶二吡咯甲烷配体（pyrdpm = 吡啶基二吡咯甲烷）的两种配合物形成了具有一维配位结构的聚合物。这些配合物形成的配位聚合物通过单晶X射线衍射、差示扫描量热法和热重分析进行了表征。这些配合物具有正方形金字塔型的配位几何结构，其顶点位置由晶体中相邻配合物的中位吡啶供体占据。探究了这些配位复合物中促进形成扩展固体的特性。对称的[Cu(pyrdpm)2]配合物由于金属中心的位阻效应，无法形成配位固体。在[Cu(cydpm)(acac)]（cydpm = 氰基二吡咯甲烷）等配合物中，使用氰基供体代替吡啶供体，也未能形成网络固体。通过这些系统性的研究，定义了这些配合物的基本配位化学以及合成此类新型配位聚合物的基本设计要求。