Abstract We herein discuss the synthesis and characterization of a novel mononuclear cobalt(II) complex CoII(TPBP)(HTMA)2 with the N-donor ligands; hexamethylenetetramine HTMA and meso-tetrakis[4-(benzoyloxy) phenylporphyrin H2TPBP. Firstly, molecular structure and supramolecular assembly have been thoroughly described. The basic core (porphyrin macrocycle) is nearly planar and the cobalt coordination centre sits in slightly distorted octahedral environment occupied by four pyrrolic nitrogen atoms (NPy) and two HTMA nitrogens (NHTMA). On the basis of quantum chemical density-functional theory calculations, metal—ligand charge-transfer interaction (MLCTI), spin density distribution and chemical reactivity character have been also highlighted. Finally, the bio-activity of free porphyrin and their cobalt complexes was evaluated in vitro, by examining their inhibitory effect against some yeasts and fungal strains, and their ability to scavenge 1,1-diphenyl-picrylhydrazyl DPPH radical. This research could provide rich insights into the structural, electronic and (bio)chemical features of analogues macrocyclic metal complexes.

中文翻译：

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具有富氮大环化合物的杂配钴 (II) 复合物 - 结构、生物活性和 DFT 建模

摘要 我们在此讨论了具有 N 供体配体的新型单核钴 (II) 配合物 CoII(TPBP)(HTMA)2 的合成和表征；六亚甲基四胺 HTMA 和内消旋四 [4-(苯甲酰氧基) 苯基卟啉 H2TPBP。首先，已经彻底描述了分子结构和超分子组装。基本核心（卟啉大环）几乎是平面的，钴配位中心位于略微扭曲的八面体环境中，由四个吡咯氮原子（NPy）和两个 HTMA 氮（NHTMA）占据。在量子化学密度泛函理论计算的基础上，还强调了金属-配体电荷转移相互作用（MLCTI）、自旋密度分布和化学反应特性。最后，在体外评估了游离卟啉及其钴配合物的生物活性，通过检查它们对一些酵母菌和真菌菌株的抑制作用，以及它们清除 1,1-二苯基-苦基肼基 DPPH 自由基的能力。这项研究可以为类似物大环金属配合物的结构、电子和（生物）化学特征提供丰富的见解。