新型多核CuII/CoII配合物由一个和两个Cu2Co三角形与反铁磁交换偶联构成

V. G. Makhankova, O. Vassilyeva, V. N. Kokozay, B. Skelton, L. Sorace, D. Gatteschi
{"title":"新型多核CuII/CoII配合物由一个和两个Cu2Co三角形与反铁磁交换偶联构成","authors":"V. G. Makhankova, O. Vassilyeva, V. N. Kokozay, B. Skelton, L. Sorace, D. Gatteschi","doi":"10.1039/B205389F","DOIUrl":null,"url":null,"abstract":"The reaction of acetonitrile solutions of CoX2·2H2O (X = NCS, I, Br) and 2-dimethylaminoethanol (HL) with copper powder in air leads to the formation of new tri- and hexa-nuclear complexes [Cu2Co(NCS)3L3]·½CH3CN (1), [Cu2Co(μ3-OH)I2L3]2·4CH3CN (2) and [Cu2Co(μ3-OH)Br2L3]2·2CH3CN (3). X-Ray crystallographic analysis of 1 reveals a symmetrical triangular core with one Co and two Cu atoms. The amino alkoxo- and SNCS-bridges between metal centres result in copper–copper and copper–cobalt separations of 3.413(2) and 3.103(2) \nA, respectively. Additional intermolecular association occurs through the NCS groups bridging Co and Cu centres of adjacent complex molecules to give chains. In the solid-state structures of 2 and 3 two symmetry-related Cu2Co units are linked by amino alkoxo bridges to form a hexanuclear molecule with intermetallic distances ranging from 3.102(2)–3.260(2) \n(Cu⋯Co) to 3.287(3)–3.931(2) \nA \n(Cu⋯Cu). The triangular planes formed by two copper and one cobalt atoms bridged by oxygen atoms from L groups are capped by a μ3-hydroxide not found in the core of 1. The hexanuclear units show no significant intermolecular contacts in the solid state. Variable-temperature magnetic susceptibility studies performed on 1 and 2 in the temperature range 5–280 K gave satisfactory fits to the observed susceptibility data by assuming isotropic magnetic exchange interactions and using the appropriate spin Hamiltonians considering 1 as a trinuclear entity and 2 as a combination of two trinuclear entities. An antiferromagnetic spin exchange operates in the Cu2Co units of both complexes [JCuCu \n= 40.1(4) \n(1), 48.7(9) \n(2); JCuCo \n= 141(2) \n(1), 86.2(1.3) cm−1 \n(2)] while a weak ferromagnetic coupling is active between Cu and Co ions from different trinuclear entities in 2 \n(JCuCo′ \n= \n−8.0(4) cm−1).","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":"21 1","pages":"4253-4259"},"PeriodicalIF":0.0000,"publicationDate":"2002-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"32","resultStr":"{\"title\":\"Novel polynuclear CuII/CoII complexes constructed from one and two Cu2Co triangles with antiferromagnetic exchange coupling\",\"authors\":\"V. G. Makhankova, O. Vassilyeva, V. N. Kokozay, B. Skelton, L. Sorace, D. Gatteschi\",\"doi\":\"10.1039/B205389F\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The reaction of acetonitrile solutions of CoX2·2H2O (X = NCS, I, Br) and 2-dimethylaminoethanol (HL) with copper powder in air leads to the formation of new tri- and hexa-nuclear complexes [Cu2Co(NCS)3L3]·½CH3CN (1), [Cu2Co(μ3-OH)I2L3]2·4CH3CN (2) and [Cu2Co(μ3-OH)Br2L3]2·2CH3CN (3). X-Ray crystallographic analysis of 1 reveals a symmetrical triangular core with one Co and two Cu atoms. The amino alkoxo- and SNCS-bridges between metal centres result in copper–copper and copper–cobalt separations of 3.413(2) and 3.103(2) \\nA, respectively. Additional intermolecular association occurs through the NCS groups bridging Co and Cu centres of adjacent complex molecules to give chains. In the solid-state structures of 2 and 3 two symmetry-related Cu2Co units are linked by amino alkoxo bridges to form a hexanuclear molecule with intermetallic distances ranging from 3.102(2)–3.260(2) \\n(Cu⋯Co) to 3.287(3)–3.931(2) \\nA \\n(Cu⋯Cu). The triangular planes formed by two copper and one cobalt atoms bridged by oxygen atoms from L groups are capped by a μ3-hydroxide not found in the core of 1. The hexanuclear units show no significant intermolecular contacts in the solid state. Variable-temperature magnetic susceptibility studies performed on 1 and 2 in the temperature range 5–280 K gave satisfactory fits to the observed susceptibility data by assuming isotropic magnetic exchange interactions and using the appropriate spin Hamiltonians considering 1 as a trinuclear entity and 2 as a combination of two trinuclear entities. An antiferromagnetic spin exchange operates in the Cu2Co units of both complexes [JCuCu \\n= 40.1(4) \\n(1), 48.7(9) \\n(2); JCuCo \\n= 141(2) \\n(1), 86.2(1.3) cm−1 \\n(2)] while a weak ferromagnetic coupling is active between Cu and Co ions from different trinuclear entities in 2 \\n(JCuCo′ \\n= \\n−8.0(4) cm−1).\",\"PeriodicalId\":17317,\"journal\":{\"name\":\"Journal of The Chemical Society-dalton Transactions\",\"volume\":\"21 1\",\"pages\":\"4253-4259\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2002-11-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"32\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of The Chemical Society-dalton Transactions\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/B205389F\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of The Chemical Society-dalton Transactions","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/B205389F","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 32

摘要

CoX2·2H2O (X = NCS, I, Br)和2-二甲氨基乙醇(HL)的乙腈溶液在空气中与铜粉反应,形成新的三核和六核配合物[Cu2Co(NCS)3L3]·½CH3CN (1), [Cu2Co(μ3-OH)I2L3]2·4CH3CN(2)和[Cu2Co(μ3-OH)Br2L3]2·2CH3CN (3). X射线晶体学分析显示1具有一个Co和两个Cu原子的对称三角形核。金属中心之间的氨基烷氧基和sncs桥分别导致铜-铜和铜-钴的分离,分别为3.413(2)A和3.103(2)A。通过NCS基团桥接相邻络合分子的Co和Cu中心形成链,还发生了分子间的结合。在2和3的固态结构中,两个对称相关的Cu2Co单元通过氨基烷氧基桥连接,形成金属间距离从3.102(2)-3.260 (2)(Cu⋯Co)到3.287(3)-3.931 (2)a (Cu⋯Cu)的六核分子。由2个铜原子和1个钴原子与L基团上的氧原子桥接而成的三角形平面被1的核心中没有的μ3-氢氧化物覆盖。六核单元在固态中没有明显的分子间接触。在5-280 K温度范围内对1和2进行了变温磁化率研究,通过假设各向同性磁交换相互作用,并考虑1为三核实体,2为两个三核实体的组合,使用适当的自旋哈密顿量,得到了满意的磁化率数据拟合。两种配合物的Cu2Co单元都发生了反铁磁自旋交换[JCuCu = 40.1(4) (1), 48.7(9) (2);JCuCo = 141(2) (1), 86.2(1.3) cm−1(2)],而来自不同三核实体的Cu和Co离子在2(JCuCo ' =−8.0(4)cm−1)之间存在弱铁磁耦合。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Novel polynuclear CuII/CoII complexes constructed from one and two Cu2Co triangles with antiferromagnetic exchange coupling
The reaction of acetonitrile solutions of CoX2·2H2O (X = NCS, I, Br) and 2-dimethylaminoethanol (HL) with copper powder in air leads to the formation of new tri- and hexa-nuclear complexes [Cu2Co(NCS)3L3]·½CH3CN (1), [Cu2Co(μ3-OH)I2L3]2·4CH3CN (2) and [Cu2Co(μ3-OH)Br2L3]2·2CH3CN (3). X-Ray crystallographic analysis of 1 reveals a symmetrical triangular core with one Co and two Cu atoms. The amino alkoxo- and SNCS-bridges between metal centres result in copper–copper and copper–cobalt separations of 3.413(2) and 3.103(2) A, respectively. Additional intermolecular association occurs through the NCS groups bridging Co and Cu centres of adjacent complex molecules to give chains. In the solid-state structures of 2 and 3 two symmetry-related Cu2Co units are linked by amino alkoxo bridges to form a hexanuclear molecule with intermetallic distances ranging from 3.102(2)–3.260(2) (Cu⋯Co) to 3.287(3)–3.931(2) A (Cu⋯Cu). The triangular planes formed by two copper and one cobalt atoms bridged by oxygen atoms from L groups are capped by a μ3-hydroxide not found in the core of 1. The hexanuclear units show no significant intermolecular contacts in the solid state. Variable-temperature magnetic susceptibility studies performed on 1 and 2 in the temperature range 5–280 K gave satisfactory fits to the observed susceptibility data by assuming isotropic magnetic exchange interactions and using the appropriate spin Hamiltonians considering 1 as a trinuclear entity and 2 as a combination of two trinuclear entities. An antiferromagnetic spin exchange operates in the Cu2Co units of both complexes [JCuCu = 40.1(4) (1), 48.7(9) (2); JCuCo = 141(2) (1), 86.2(1.3) cm−1 (2)] while a weak ferromagnetic coupling is active between Cu and Co ions from different trinuclear entities in 2 (JCuCo′ = −8.0(4) cm−1).
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
自引率
0.00%
发文量
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信