Synthesis and design of paramagnetic metal complexes containing stable radicals and their spectroscopic study

本研究旨在研究金属配合物与自由基配体之间交换偶联的通用性和微调性，以及配体场与自由基之间的电子和磁性相互作用，以及自由基配合物在溶液中的反应性，主要目的是合成和设计含自由基配体的顺磁性金属配合物。首先，我们揭示了由于配体场的微妙变化而引起的d电子态的行为，如通过核磁共振和溶剂变色观察到的溶剂效应，以及由于各向异性pi键引起的反常三角场分裂。此外，我们还探讨了由于氢键和CH/pi相互作用等弱分子内相互作用引起的空间效应。这些研究是重要和基本信息检查之间的配位键金属和激进,特别是在d轨道和π^ *轨道(SOMO)其次,激进的复合物的顺磁金属铬(III)和镍(II)等[Cr(中航商用飞机有限公司)_2 (NIT2-py)] +或(Ni (dbm) _2 (NIT2-py)] (dbm = dibenzoylmethane)和抗磁有限公司(III)金属如反式-(有限公司(中航商用飞机有限公司)_2 (X) (NIT4 + py)) ^ n (X = PPh_3: n = 1 +;你< 2 >:n = 0))和反式-(股份有限公司(中航商用飞机有限公司)_2 (P (Ph_3)) (4-NH_2tempo)] +已准备。研究了它们的稳定性和磁光特性，如自旋禁止跃迁的强度增强。反式[Co(acac)_2(PPh_3)(NIT4-py)]+的x射线结构分析证实了其吡啶配位模式。这些数据将是实现本研究目的的重要线索，对自由基配合物的化学研究具有重要价值。

This research aims at versatility and fine-tuning of the exchange coupling between metal complexes and radical ligands together with electronic and magnetic interaction between the ligand field and radicals as well as the reactivity of radical complexes in solutions for the primary purpose of synthesis and design of paramagnetic metal complexes containing radical ligands.Firstly, we have revealed the behavior or the d electron state due to the subtle change of the ligand field such as the solvent effects as observed for the NMR and solvatochromism as well as anomalous trigonal field splitting due to anisotropic pi bonding. Furthermore, we explored the steric effect due to weak intramolecular interactions such as hydrogen bond and CH/pi interaction. These studies are the important and basic information to examine the coordination bond between the metal and radical, especially between the d orbital and pi^* orbital (SOMO)Secondarily, radical complexes of paramagnetic Cr(III) and Ni(II) metal such as [Cr(acac)_2(NIT2-py)]+or[Ni(dbm)_2(NIT2-py)](dbm=dibenzoylmethane) and those of diamagnetic Co(III) metal such as trans-[Co(acac)_2(X)(NIT4+py)]^n(X=PPh_3 : n=1+ ; NO_<-2> : n=0)) and trans-[Co(acac)_2(P(Ph_3))(4-NH_2tempo)]+have been prepared. Their stability and magneto-optic properties such as the intensity enhancement of the spin-forbidden transitions were examined. The X-ray structure analysis of trans-[Co(acac)_2(PPh_3)(NIT4-py)]+confirmed the pyridine coordination mode. These data will be an important clue to accomplish the present purpose and valuable for the chemistry for radical complexes.