Journal of Inclusion Phenomena and Macrocyclic Chemistry ( IF 1.7 ) Pub Date : 2023-06-13 , DOI: 10.1007/s10847-023-01191-4 Ravinder , Dipak Kumar Das , Anuj Kumar
The monitoring of shifting of the redox potential of macrocyclic complexes towards anodic or cathodic regions, which acts as a mediator in many electrocatalytic events, is made possible by inserting electron donating or electron withdrawing group into their frameworks. Herein, using a template strategy, two [14]-membered N4-macrocyclic complexes (denoted as complex A and complex B) with similar molecular cores but different phenyl moieties were prepared and characterized using multiple characterization techniques. The characterization results suggested a saddle-shaped geometry for these complexes, which might be due to the steric repulsions between the benzenoid and amidic moieties on the macrocyclic framework, as also supported by theoretical computations. Further, to investigate the electrochemical behaviors of these complexes, cyclic voltammetry was used and found that the Fe3+/2+ redox potential was systematically shifted in anodic direction with the increment of phenyl moieties on the [14]-membered N4-macrocyclic core. DFT calculations indicated the down-shifting in the most occupied molecular orbital due to the increased phenyl conjugation, which could be correlated with the shifting of Fe3+/2+ redox potential. Biological evaluation of these complexes has also been carried out.
中文翻译:
苯基共轭对 FeN4-丙烯酸配合物 Fe3+/2+ 形式电位的影响
通过在其框架中插入供电子或吸电子基团,可以监测大环配合物的氧化还原电位向阳极或阴极区域的转移,阳极或阴极区域在许多电催化事件中充当中介。在此,使用模板策略,两个[14]-成员N 4制备了具有相似分子核但苯基部分不同的大环复合物(表示为复合物 A 和复合物 B),并使用多种表征技术对其进行了表征。表征结果表明这些配合物具有马鞍形几何形状,这可能是由于大环骨架上的苯环和酰胺部分之间的空间排斥,理论计算也支持这一点。此外,为了研究这些配合物的电化学行为,使用循环伏安法发现 Fe 3+/2+氧化还原电位随着 [14] 元 N 4上苯基部分的增加而系统地向阳极方向移动-大环核心。DFT 计算表明,由于苯基共轭增加,最多被占据的分子轨道向下移动,这可能与 Fe 3+/2+氧化还原电势的移动相关。还对这些复合物进行了生物学评价。