Extreme g-Tensor Anisotropy and Its Insensitivity to Structural Distortions in a Family of Linear Two-Coordinate Ni(I) Bis-N-heterocyclic Carbene Complexes
Extreme g-Tensor Anisotropy and Its Insensitivity to Structural Distortions in a Family of Linear Two-Coordinate Ni(I) Bis-N-heterocyclic Carbene Complexes
复制标题
一族线性二配位 Ni(I) 双-N-杂环卡宾配合物中的极端 g 张量各向异性及其对结构变形的不敏感性
DOI：
10.1021/acs.inorgchem.1c02413
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发表时间：
2022
影响因子：
4.6
通讯作者：
William J. M. Blackaby, Katie L.
中科院分区：
文献类型：
--
作者：
William J. M. Blackaby, Katie L.
本文报道了一系列新的均配型Ni（I）双N杂环卡宾配合物，其两个配体间的扭转角为68° ~ 90°。电子顺磁共振测量结果表明，在所有的配合物与小的变化范围为5.7-5.9和g = 0.6的各向异性强张量。通过可变场远红外磁谱和SOC-CASSCF/NEVPT 2计算确定的第一激发态的能量在270-650 cm-1的范围内。在10 K以下，用交流磁化率测量的磁弛豫主要是拉曼过程和直接过程，从头算配位场分析表明，扭转角<90°时，双占据dxz和dyz轨道发生分裂，这对磁性质影响不大，而磁弛豫的温度依赖性与扭转角无关.
We report a new series of homoleptic Ni(I) bis-N-heterocyclic carbene complexes with a range of torsion angles between the two ligands from 68° to 90°. Electron paramagnetic resonance measurements revealed a strongly anisotropicg-tensor in all complexes with a small variation ing∥∼ 5.7–5.9 andg⊥∼ 0.6. The energy of the first excited state identified by variable-field far-infrared magnetic spectroscopy and SOC-CASSCF/NEVPT2 calculations is in the range 270–650 cm–1. Magnetic relaxation measured by alternating current susceptibility up to 10 K is dominated by Raman and direct processes.Ab initioligand-field analysis reveals that a torsion angle of <90° causes the splitting between doubly occupied dxzand dyzorbitals, which has little effect on the magnetic properties, while the temperature dependence of the magnetic relaxation appears to have no correlation with the torsion angle.