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本文报道了1个基于3,8-二噻吩-1,10-菲啰啉(dtphen)的双核锰(Ⅱ)配合物1[trans-Mn2Cl4(dtphen)2]和2个基于3,8-二甲基噻吩-1,10-菲啰啉(dmtphen)的单核锰(Ⅱ)和单核钴(Ⅱ)配合物2和3(分子式分别为[cis-MnCl2(dmtphen)2]和[cis-CoCl2(dmtphen)2])的合成、波谱和晶体结构表征。其中,2个锰(Ⅱ)配合物的分子结构呈现不同的配位模式,由于噻吩环上甲基引入所产生的位阻效应,导致单核配合物2和3中,两配体中的噻吩环相对于1,10-菲啰啉环呈现相同的反式/反式分子构型,其二面角分布在14.1(1)°~51.5(1)°。而对于双核配合物1,由于没有甲基位阻的影响,其相应芳环之间二面角减少至2.0(1)°~20.2(1)°,且配体呈现顺式/反式分子构型。
In this paper, we report a binary complex of trans-Mn2Cl4 (dtphen) 2 based on 3-dodecene-1,10-phenanthroline (dtphen) Mn (dmtphen) 2] and [cis-MnCl2 (dmtphen) 2] complexes of mononuclear manganese (Ⅱ) and mononuclear cobalt (Ⅱ) CoCl2 (dmtphen) 2]), spectroscopy and crystal structure characterization. Among them, the molecular structures of the two manganese (Ⅱ) complexes show different coordination modes. The steric hindrance caused by the introduction of methyl groups on the thiophene ring leads to the formation of thiophenes in the two ligands in mononuclear complexes 2 and 3 The ring exhibits the same trans / trans molecular configuration relative to the 1,10-phenanthroline ring and has a dihedral angle of 14.1 (1) ° to 51.5 ° (1 °). In the case of binuclear complex 1, the dihedral angle between the corresponding aromatic rings decreases to 2.0 (1) ° to 20.2 (1) ° due to the absence of methyl group steric hindrance, and the ligand exhibits cis / trans molecular structure type.