当前位置：
X-MOL 学术
›
Inorg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Spectroscopic Investigation of Interaction between the 4f Electronic System and the Photoexcited Cyclic π System in Terbium(III) Monoporphyrinato Complex.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-09-22 , DOI: 10.1021/acs.inorgchem.0c02107 Anas Santria 1 , Naoto Ishikawa 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-09-22 , DOI: 10.1021/acs.inorgchem.0c02107 Anas Santria 1 , Naoto Ishikawa 1
Affiliation
|
Electronic interaction between the total angular momentum (J) of the 4f electronic system and an angular momentum (L) of the photoexcited cyclic π system in a terbium(III) monoporphyrinato complex with a capping ligand cyclen, [Tb(TPP)(cyclen)]Cl (TPP = 5,10,15,20-tetraphenylporphyrinato; cyclen = 1,4,7,10-tetraazacyclododecane), have been investigated by varied-temperature and varied-magnetic-field magnetic circular dichroism (MCD) spectroscopy. Three MCD A-term patterns which correspond to B(0,0), Q(0,0), and Q(1,0) absorption bands were observed for the complex which was incorporated into a thin film of poly(methyl methacrylate), PMMA, as well as that in solution phase. The A-term patterns in the Soret band region and Q-band region were found to show opposite behavior with changes in temperature and magnetic field. This finding clearly indicated not only the presence of the J–L interaction but also the different directions of the J–L interaction; i.e., J and L interact ferromagnetically in the Q(0,0) and Q(1,0) states, while antiferromagnetically in the B(0,0) state. The magnitude of the interaction was determined by simulation-based fitting to experimental 
ratios, where 
refers to the A-term intensity and 
to the oscillator strength of the band. The first ab initio study was also carried out for further insight into the interaction. From the computational study, the relationship between the orbital angular momentum of π electronic system, L(π), and the orbital angular momentum of the 4f system, L(f), was clearly revealed. A computational approach to determine the magnitude and the direction of J–L interaction was established.
中文翻译：
f（III）单卟啉络合物中4f电子系统与光激发环π系统相互作用的光谱研究。
4f电子系统的总角动量（J）和角动量（L）的光激发环π系统在具有封端配体cycln [Tb（TPP）（cycln）] Cl（TPP = 5,10,15,20-tetraphenylporphyrinato; cyclen = 1,4， 7,10-四氮杂环十二烷），已通过温度变化和磁场圆二色性（MCD）光谱进行了研究。对于掺入到聚（甲基丙烯酸甲酯）薄膜中的络合物，观察到三个对应于B（0,0），Q（0,0）和Q（1,0）吸收带的MCD A项模式。 ，PMMA以及溶液阶段。发现Soret带区域和Q带区域中的A项模式在温度和磁场的变化下表现出相反的行为。这一发现清楚地表明，不仅J - L相互作用，以及J - L相互作用的不同方向；即，J和L在Q（0,0）和Q（1,0）状态下铁磁性相互作用，而在B（0,0）状态下反铁磁性相互作用。相互作用的大小由基于模拟的对实验比率的拟合确定，该比率指的是A项强度和频带的振荡器强度。还进行了第一次从头开始研究，以进一步了解相互作用。通过计算研究，π电子系统的轨道角动量L之间的关系（π），并且清楚地显示了4f系统的轨道角动量L（f）。建立了确定J - L相互作用的大小和方向的计算方法。
更新日期：2020-10-05
ratios, where refers to the A-term intensity and to the oscillator strength of the band. The first ab initio study was also carried out for further insight into the interaction. From the computational study, the relationship between the orbital angular momentum of π electronic system, L(π), and the orbital angular momentum of the 4f system, L(f), was clearly revealed. A computational approach to determine the magnitude and the direction of J–L interaction was established.
中文翻译：
f（III）单卟啉络合物中4f电子系统与光激发环π系统相互作用的光谱研究。
4f电子系统的总角动量（J）和角动量（L）的光激发环π系统在具有封端配体cycln [Tb（TPP）（cycln）] Cl（TPP = 5,10,15,20-tetraphenylporphyrinato; cyclen = 1,4， 7,10-四氮杂环十二烷），已通过温度变化和磁场圆二色性（MCD）光谱进行了研究。对于掺入到聚（甲基丙烯酸甲酯）薄膜中的络合物，观察到三个对应于B（0,0），Q（0,0）和Q（1,0）吸收带的MCD A项模式。 ，PMMA以及溶液阶段。发现Soret带区域和Q带区域中的A项模式在温度和磁场的变化下表现出相反的行为。这一发现清楚地表明，不仅J - L相互作用，以及J - L相互作用的不同方向；即，J和L在Q（0,0）和Q（1,0）状态下铁磁性相互作用，而在B（0,0）状态下反铁磁性相互作用。相互作用的大小由基于模拟的对实验
比率的拟合确定，该比率指的是A项强度和频带的振荡器强度。还进行了第一次从头开始研究，以进一步了解相互作用。通过计算研究，π电子系统的轨道角动量L之间的关系（π），并且清楚地显示了4f系统的轨道角动量L（f）。建立了确定J - L相互作用的大小和方向的计算方法。
京公网安备 11010802027423号