有机磺酸根阴离子调控的[Co (pytpy)2]2+自旋交叉化合物
Spin crossover in [Co(pytpy)2]2+ complexes modified by organosulfonate anions
作者单位E-mail
李英莲 南京大学化学化工学院, 配位化学国家重点实验室, 南京 210023  
张诚诚 南京大学化学化工学院, 配位化学国家重点实验室, 南京 210023  
张新宇 南京大学化学化工学院, 配位化学国家重点实验室, 南京 210023  
王新益 南京大学化学化工学院, 配位化学国家重点实验室, 南京 210023 wangxy66@nju.edu.cn 
摘要: 本文报道了2例由有机磺酸根阴离子调控的单核钴(Ⅱ)配合物[Co(pytpy)2](2-NH2-1-NS)2·MeOH·H2O (1)和[Co(pytpy)2](4-NH2-1-NS)2·H2O (2)的合成、晶体结构和磁性,其中pytpy=4'-(4-吡啶基)-2,2'∶6',2″-三联吡啶,2-NH2-1-NS-=2-氨基-1-萘磺酸根离子,4-NH2-1-NS-=4-氨基-1-萘磺酸根离子。单晶X射线衍射分析表明,这2例配合物均由[Co(pytpy)2]2+阳离子、有机磺酸根阴离子和结晶溶剂分子组成。其中,阴离子2-NH2-1-NS-和4-NH2-1-NS-仅在磺酸根和氨基的相对位置上有所不同。有趣的是,具有处于邻位的磺酸根和氨基的2-NH2-1-NS-阴离子与[Co(pytpy)2]2+阳离子和溶剂分子形成氢键,而具有处于对位的磺酸根和氨基的4-NH2-1-NS-阴离子之间通过氢键形成了二维层状结构。磁测量表明配合物12的磁性有很大的不同:配合物1具有可逆的渐变型自旋交叉行为,而化合物2则保持在高自旋态。
关键词: 自旋交叉  二价钴配合物  有机磺酸根阴离子  氢键
基金项目: 国家自然科学基金(No.22273036,21973039)资助。
Abstract: Two mononuclear cobalt(Ⅱ) complexes, [Co(pytpy)2](2-NH2-1-NS)2·MeOH·H2O (1) and [Co(pytpy)2](4-NH2-1-NS)2·H2O (2), where pytpy=4'-(4-pyridyl)-2,2'∶6',2″-terpyridine, 2-NH2-1-NS-=2-amino-1-naphthalenesulfonate, and 4-NH2-1-NS-=4-amino-1-naphthalenesulfonate, were synthesized and characterized structurally and magnetically. Single-crystal X-ray analysis reveals that both complexes consist of the [Co(pytpy)2]2+ cations, organosulfonate anions, and crystallized solvent molecules. The difference between the two anions is the relative position of the sulfonate and amino groups. Interestingly, the 2-NH2-1-NS- anion with the sulfonate and amino group in adjacent positions, forms hydrogen bonds with the [Co(pytpy)2]2+ cation and solvent molecules, while the 4-NH2-1-NS- anion, with the sulfonate and amino groups in para positions, forms a 2D layer structure through hydrogen bonding. Magnetic measurements revealed significant differences in their magnetic properties: while complex 1 exhibits a reversible and gradual spin crossover behavior, complex 2 remains in the high-spin state.
Keywords: spin crossover  Co (Ⅱ) complex  organosulfonate anion  hydrogen bond
投稿时间:2024-03-20 修订日期:2024-04-20
摘要点击次数:  140
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李英莲,张诚诚,张新宇,王新益.有机磺酸根阴离子调控的[Co (pytpy)2]2+自旋交叉化合物[J].无机化学学报,2024,40(6):1162-1172.
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