基于氮氧自由基配体的锰和钴双核配合物的分子结构和磁性  

Crystal structures and magnetic properties of manganese and cobalt binuclear complexes based on nitroxide radical

作　　者：冯勋[1] 方海鹏 安杨 张策 陈雪怡 郭博文 FENG Xun;FANG Haipeng;AN Yang;ZHANG Ce;CHEN Xueyi;GUO Bowen(College of Chemistry and Chemical Engineering and Henan Key Laboratory of Function Oriented Porous Materials,Luoyang Normal University,Luoyang,Henan 471934,China;Green Catalysis Center,and College of Chemistry,Zhengzhou University,Zhengzhou 450001,China;College of Chemistry and Pharmacy Engineering,Nanyang Normal University,Nanyang,Henan 473601,China)

机构地区：[1]洛阳师范学院化学与化工学院,河南省功能导向多孔材料重点实验室,洛阳471934 [2]郑州大学绿色催化中心和化学学院,郑州450001 [3]南阳师范学院化学与制药工程学院,南阳473601

出　　处：《无机化学学报》2024年第2期421-429,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22371110);河南省高校科技创新人才计划(No.21IRTSTHN004)资助。

摘　　要：合成了2个基于氮氧自由基配体且结构类似的双核配位化合物,其分子式分别为[Mn_(2)(hfac)_(4)(NIT-mo-pmy)_(2)](1)和[Co_(2)(hfac)_(4)(NIT-mo-pmy)_(2)](2),其中hfac=六氟乙酰丙酮,NIT-mo-pmy=2-(2-甲氧基-5’-嘧啶基)-4,4,5,5-四甲基咪唑啉基-3-氧-1-氧自由基。2个配合物均属于三斜晶系P1空间群,其双核配位单元进一步构筑为中心对称的平行四边形分子阵列。变温磁化率的测试表明,在2个配合物中,中心离子和氮氧自由基单元之间存在反铁磁交换作用。借助构效关系研究,分析了磁作用强度的差异。通过适当近似的磁化学模型,对Mn(Ⅱ)配合物的磁性行为进行了定量拟合,并与相关化合物磁作用强度进行了比对、分析。Two analogous binuclear coordination complexes derived from nitronyl nitroxide radical ligands have been synthesized.Their general formulae are[Mn_(2)(hfac)_(4)(NIT-mo-pmy)_(2)](1)and[Co_(2)(hfac)_(4)(NIT-mo-pmy)_(2)](2),respectively,where hfac=hexafluoroacetylacetone and NIT-mo-pmy=2-(2-methoxy-5′-pyrimidinyl)-4,4,5,5-tetramethyl-imidazoline-3-oxy-1-oxyl radical.Both complexes crystallize in a triclinic system P1 space group,exhibiting a centrosymmetric rectangle-like array based on dimer coordination units.Variable-temperature magnetic characterizations reveal the presence of antiferromagnetic exchanges between central ions and nitroxide radicals in both fourspin nitroxide radical complexes.The different strengths of both complexes were investigated based on structureproperty relationship analysis.The magnetic behaviors of the Mncomplex have been quantitatively evaluated through an appropriate magnetic model and were compared with the relevant complexes.

关 键 词：锰(Ⅱ)配合物 钴(Ⅱ)配合物 晶体结构 NIT-mo-pmy自由基配体 反铁磁相互作用 

分 类 号：O614.711[理学—无机化学] O614.812[理学—化学]