Magnetic interaction of photoexcited terbium?porphyrin complexes with non-aromatic ligands having different symmetries
Magnetic interaction of photoexcited terbium?porphyrin complexes with non-aromatic ligands having different symmetries
复制标题
光激发铽卟啉配合物与不同对称性非芳香配体的磁相互作用
DOI：
10.1039/d2dt00306f
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发表时间：
2022
影响因子：
4
通讯作者：
Ishikawa Naoto
中科院分区：
文献类型：
--
作者：
Adi Langit Cahya;Santria Anas;Ishikawa Naoto
利用温度依赖和磁圆二色性（MCD）研究了镧系元素中4f电子的总角动量(J)与卟啉在光激发态的轨道角动量(L)之间的相互作用，研究了5,10,15,20-四苯基卟啉（TPP）铽（III）配合物与两种不同的非芳配体即12-冠-4（1,4,7,10-四氧环十二烷）和1-氮杂-12-冠-4（1,4,7-三氧-10-氮杂环十二烷）。研究了两种不同配体的情况，以了解磁相互作用如何依赖于非芳香配体的对称性。可见光区B（0,0）、Q（1,0）和Q（0,0）三个吸收带显示温度相关的MCD A项。对于每个波段，J-L相互作用由基于模拟的拟合与实验比率确定。当第二配体为对称性较低的氮杂冠时，J-L相互作用的强度增加。通过从头算RASSCF/RASSI计算，探讨了第二配体对配体中心激发态的差异和配体场分裂结构对J = 6的金属中心基多倍体的影响。
Interaction between the total angular momentum (J) of 4f electrons in lanthanides and the orbital angular momentum (L) of porphyrins in the photoexcited states was investigated by temperature-dependent and magnetic circular dichroism (MCD) for 5,10,15,20-tetraphenylporphyrinato (TPP) terbium(III) complexes with two different non-aromatic ligands i.e. 12-crown-4(1,4,7,10-tetraoxacyclododecane) and 1-aza-12-crown-4(1,4,7-trioxa-10-azacyclododecane). The two cases with different ligands were examined in order to understand how magnetic interaction depends on the symmetry of the non-aromatic ligands. The three absorption bands in the visible region, B(0,0), Q(1,0), and Q(0,0) bands, showed temperature-dependent MCD A term. For each band, the J–L interaction was determined from the simulation-based fitting to experimental ratios. An increase in the magnitude of the J–L interaction was observed when the second ligand was the aza-crown with a lower symmetry. Ab initio RASSCF/RASSI calculations were performed to explore the effect of the difference in the second ligand to the ligand centred excited states and the ligand-field-splitting structure on the metal-centred ground multiplet of J = 6.