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：李英莲 张诚诚 张新宇 王新益 LI Yinglian;ZHANG Chengcheng;ZHANG Xinyu;WANG Xinyi(State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China)

机构地区：[1]南京大学化学化工学院,配位化学国家重点实验室,南京210023

出　　处：《无机化学学报》2024年第6期1162-1172,共11页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22273036,21973039)资助。

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-NH_(2)-1-NS)_(2)·MeOH·H_(2)O(1)和[Co(pytpy)_(2)](4-NH_(2)-1-NS)2·H_(2)O(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-NH_(2)-1-NS-=2-氨基-1-萘磺酸根离子,4-NH_(2)-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-NH_(2)-1-NS-和4-NH_(2)-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-NH_(2)-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-NH_(2)-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1和2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。Two mononuclear cobaltcomplexes,[Co(pytpy)_(2)](2-NH_(2)-1-NS)_(2)·MeOH·H_(2)O(1)and[Co(pytpy)_(2)](4-NH_(2)-1-NS)_(2)·H_(2)O(2),where pytpy=4'-(4-pyridyl)-2,2'∶6',2″-terpyridine,2-NH_(2)-1-NS-=2-amino-1-naphthalenesulfonate,and 4-NH_(2)-1-NS-=4-amino-1-naphthalenesulfonate,were synthesized and characterized structurally and magnetical-ly.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 sulfo-nate and amino groups.Interestingly,the 2-NH_(2)-1-NS-anion with the sulfonate and amino group in adjacent posi-tions,forms hydrogen bonds with the[Co(pytpy)_(2)]^(2+)cation and solvent molecules,while the 4-NH_(2)-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.CCDC:2270460,1;2270462,2.

关 键 词：自旋交叉 二价钴配合物 有机磺酸根阴离子 氢键 

分 类 号：O614.812[理学—无机化学]