Halper Sara R, Malachowski Mitchell R, Delaney Heather M, Cohen Seth M
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0358, USA.
Inorg Chem. 2004 Feb 23;43(4):1242-9. doi: 10.1021/ic0352295.
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.
本文介绍了中性[Cu(dpm)₂]和[Cu(dpm)(acac)]（dpm = 二吡咯亚甲基，acac = 乙酰丙酮）配合物的合成。通过电子吸收光谱和红外光谱监测不对称金属配合物的形成。所研究的两种配合物含有吡啶二吡咯亚甲基配体（pyrdpm = 吡啶基二吡咯亚甲基），形成一维配位聚合物。这些配合物形成的配位聚合物已通过单晶X射线衍射、差示扫描量热法和热重分析进行了表征。这些配合物具有四方锥配位几何结构，晶格中相邻配合物的中吡啶基供体占据顶端位置。已对这些配位配合物中有助于形成扩展固体的特征进行了探究。对称的[Cu(pyrdpm)₂]配合物由于金属中心的空间位阻而无法形成配位固体。在诸如[Cu(cydpm)(acac)]（cydpm = 氰基二吡咯亚甲基）的配合物中使用氰基供体代替吡啶基供体也无法形成网络固体。通过这些系统研究，已确定了这些配合物的基本配位化学以及合成这类新型配位聚合物的基本设计要求。
