酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性

引用本文: 谢齐威, 崔爱莉, 寇会忠. 酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性[J]. 无机化学学报, 2015, 31(9): 1798-1804. doi: 10.11862/CJIC.2015.219 shu

Citation: XIE Qi-Wei, CUI Ai-Li, KOU Hui-Zhong. Synthesis, Structure and Magnetic Properties of Phenoxo-Bridged Polynuclear Cu(Ⅱ) Complexes[J]. Chinese Journal of Inorganic Chemistry, 2015, 31(9): 1798-1804. doi: 10.11862/CJIC.2015.219 shu

酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性

1.
清华大学化学系, 北京 100084

通讯作者: 寇会忠,E-mail:kouhz@mail.tsinghua.edu.cn

基金项目:
国家重点基础研究发展计划(No.2013CB933403) (No.2013CB933403)

国家自然科学基金(No.91222104,21771103,20121318518)资助项目。 (No.91222104,21771103,20121318518)

摘要: 利用柔性酚胺类配体N,N'-二甲基-N,N'-(2-羟基-4,5-二甲基苄基)乙二胺(H₂L)与Cu(Ⅱ)反应,合成了2个新的酚氧桥联多核Cu(Ⅱ)配合物[Cu₃^II(L)₂(CH₃OH)₂](ClO₄)₂(1),[Cu₃^II(L)₂(Cu^ICl₂)₂](2)。配合物1~2中,3个Cu²⁺之间通过2个酚氧桥连接,形成线性三核结构。两边的铜离子分别被配体L^2-上的N₂O₂螯合配位,轴向与甲醇分子的氧(配合物1)或[CuCl₂]^-的氯(配合物2)配位,形成四方锥配位构型。中间铜离子与两侧L^2-上的4个酚氧原子以平面四边形配位。Cu^II-O-Cu^II键角为100.14°~101.79°。对配合物1~2进行变温磁化率测量表明,铜离子之间通过酚氧桥存在强的反铁磁耦合,磁耦合常数J分别为-277(9)cm^-1(配合物1)和-299(3)cm^-1(配合物2)(基于自旋哈密顿算符Ĥ=-2J(Ŝ₁·Ŝ₂+Ŝ₂·Ŝ₃)。J值与酚氧桥桥联键角有一定相关性,即Cu-O-Cu桥联键角越大,反铁磁耦合越强。

关键词:

柔性配体;铜;多核配合物;磁性;混合价

English

Synthesis, Structure and Magnetic Properties of Phenoxo-Bridged Polynuclear Cu(Ⅱ) Complexes

1.
Department of Chemistry, Tsinghua University, Beijing 100084, China

Corresponding author: 寇会忠,E-mail:kouhz@mail.tsinghua.edu.cn

Received Date: 07 May 2014
Fund Project:
国家重点基础研究发展计划(No.2013CB933403)

国家自然科学基金(No.91222104,21771103,20121318518)资助项目。

Abstract: Two polynuclear copper complexes containing the flexible ligand N, N'-dimethyl-N, N'-(2-hydroxy-4, 5-dimethylbenzyl)ethylenediamine (H₂L) have been prepared and characterized structurally and magnetically. The complexes have the formula [Cu₃^II(L)₂(CH₃OH)₂](ClO₄)₂(1) and [Cu₃^II(L)₂(Cu^ICl₂)₂](2). X-ray single-crystal structure analyses show that both complexes contain linear Cu^II-Cu^II-Cu^II cores where adjacent Cu(Ⅱ) ions are doubly bridged by phenolate groups of L^2-. The coordination sphere of the terminal Cu(Ⅱ) ions is square pyramidal with the methanol oxygen (complex 1) or the chloride ion of [CuCl₂]^- (complex 2) situated at the apical position, whereas the central Cu(Ⅱ) has a square coordination environment. The Cu^II-O-Cu^II bridging bond angles are in the range of 100.14°~101.79°. Magnetic studies show that both complexes exhibit strong antiferromagnetic interaction with the spin exchange coupling constants (J) of -277(9) cm^-1 (1) and -299(3) cm^-1 (2) (Ĥ=-2J(Ŝ₁·Ŝ₂+Ŝ₂·Ŝ₃). The antiferromagnetic interactions have been found to be mainly related to the Cu^II-O-Cu^II bond angles. Larger Cu-O-Cu bond angles correspond to stronger antiferromagnetic interaction (more negative J values).

Key words:

flexible ligand;copper;polynuclear;magnetism;mixed-valent

1. [1] Kahn O. Molecular Magnetism. New York:VCH, 1993.[1] Kahn O. Molecular Magnetism. New York:VCH, 1993.
2. [2] GAO En-Qing(高恩庆),LIAO Dai-Zheng(廖代正). Chem. J. Chinese Universties(高等学校化学学报), 1999,20(8):1179-1185[2] GAO En-Qing(高恩庆),LIAO Dai-Zheng(廖代正). Chem. J. Chinese Universties(高等学校化学学报), 1999,20(8):1179-1185
3. [3] GAO Song(高松), BAI Ou(白欧), YI Tao(易涛), et al. Acta Chim. Sinica(化学学报), 2000,58(12):1666-1669[3] GAO Song(高松), BAI Ou(白欧), YI Tao(易涛), et al. Acta Chim. Sinica(化学学报), 2000,58(12):1666-1669
4. [4] FENG Xiao-Jia(冯小佳), LI Yang-Guang(李阳光), ZHANG Zhi-Ming(张志明), et al. Acta Chim. Sinica(化学学报), 2013,71(12):1575-1588[4] FENG Xiao-Jia(冯小佳), LI Yang-Guang(李阳光), ZHANG Zhi-Ming(张志明), et al. Acta Chim. Sinica(化学学报), 2013,71(12):1575-1588
5. [5] LIN Shuang-Yan(林双燕), GUO Yun-Nan(郭云南), XU Gong-Feng(许公峰), et al. Chinese J. Appl. Chem. (应用化学), 2010,27(12):1365-1371[5] LIN Shuang-Yan(林双燕), GUO Yun-Nan(郭云南), XU Gong-Feng(许公峰), et al. Chinese J. Appl. Chem. (应用化学), 2010,27(12):1365-1371
6. [6] WANG Qing-Lun(王庆伦), LIAO Dai-Zheng(廖代正). Prog. Chem.(化学进展), 2003,15(3):161-169[6] WANG Qing-Lun(王庆伦), LIAO Dai-Zheng(廖代正). Prog. Chem.(化学进展), 2003,15(3):161-169
7. [7] WANG Tian-Wei(王天维), LIN Xiao-Ju(林小驹), WEI Ji-Zong(韦吉宗), et al. Chinese J. Inorg. Chem.(无机化学学报), 2002,18(11):1071-1080[7] WANG Tian-Wei(王天维), LIN Xiao-Ju(林小驹), WEI Ji-Zong(韦吉宗), et al. Chinese J. Inorg. Chem.(无机化学学报), 2002,18(11):1071-1080
8. [8] LIANG Shu-Hui(梁淑惠), CHE Yun-Xia(车云霞), ZHENG Ji-Min(郑吉民). Chinese J. Inorg. Chem.(无机化学学报), 2005,21(7):1035-1038[8] LIANG Shu-Hui(梁淑惠), CHE Yun-Xia(车云霞), ZHENG Ji-Min(郑吉民). Chinese J. Inorg. Chem.(无机化学学报), 2005,21(7):1035-1038
9. [9] LU Tong-Bu(鲁统部), XIANG Hua(向华), LI Xiao-Yan (李晓燕), et al. Chem. J. Chinese Universities(高等学校化学学报), 2000,21(2):187-189[9] LU Tong-Bu(鲁统部), XIANG Hua(向华), LI Xiao-Yan (李晓燕), et al. Chem. J. Chinese Universities(高等学校化学学报), 2000,21(2):187-189
10. [10] Fu D G, Chen J, Tan X S, et al. Inorg. Chem., 1997,36:220-225[10] Fu D G, Chen J, Tan X S, et al. Inorg. Chem., 1997,36:220-225
11. [11] Kou H Z, Gao S, Zhang J, et al. J. Am. Chem. Soc., 2001, 123:11809-11810[11] Kou H Z, Gao S, Zhang J, et al. J. Am. Chem. Soc., 2001, 123:11809-11810
12. [12] CHENG Peng(程鹏), LIAO Dai-Zheng(廖代正), YAN Shi-Ping(闫世平), et al. Chemistry (化学通报), 1995,58(8):51-52[12] CHENG Peng(程鹏), LIAO Dai-Zheng(廖代正), YAN Shi-Ping(闫世平), et al. Chemistry (化学通报), 1995,58(8):51-52
13. [13] Bai Y L, Tangoulis V, Huang R B, et al. Chem. Eur. J., 2009,15:23772383[13] Bai Y L, Tangoulis V, Huang R B, et al. Chem. Eur. J., 2009,15:23772383
14. [14] WANG Qing-Lun(王庆伦), LIAO Dai-Zheng(廖代正). Chem. Res. (化学研究), 2003,14(2):74-80[14] WANG Qing-Lun(王庆伦), LIAO Dai-Zheng(廖代正). Chem. Res. (化学研究), 2003,14(2):74-80
15. [15] Tshuva E T, Gendeziuk N, Kol M. Tetrahedron Lett., 2001, 42:6405-6407[15] Tshuva E T, Gendeziuk N, Kol M. Tetrahedron Lett., 2001, 42:6405-6407
16. [16] Sheldrick G M. SHELXS-97, Program for Automatic Solution of Crystal Structure, University of Göttingen, German, 1997.[16] Sheldrick G M. SHELXS-97, Program for Automatic Solution of Crystal Structure, University of Göttingen, German, 1997.
17. [17] Sheldrick G M. SHELXL-97, Program for Crystal Structure Refinement, University of Göttingen, German, 1997.[17] Sheldrick G M. SHELXL-97, Program for Crystal Structure Refinement, University of Göttingen, German, 1997.
18. [18] Xie Q W, Chen X, Hu K Q, et al. Polyhedron, 2012,38:213-217[18] Xie Q W, Chen X, Hu K Q, et al. Polyhedron, 2012,38:213-217
19. [19] Song Y F, Gamez P, Roubeau O, et al. Eur. J. Inorg. Chem., 2003:2924-2928[19] Song Y F, Gamez P, Roubeau O, et al. Eur. J. Inorg. Chem., 2003:2924-2928
20. [20] Song Y F, Gamez P, Roubeau O, et al. Inorg. Chim. Acta, 2005,358:109-115[20] Song Y F, Gamez P, Roubeau O, et al. Inorg. Chim. Acta, 2005,358:109-115
21. [21] Song Y F, Albada G A, Quesada M, et al. Inorg. Chem. Commun., 2005,8:975-978[21] Song Y F, Albada G A, Quesada M, et al. Inorg. Chem. Commun., 2005,8:975-978
22. [22] Cui Y, Chen J, Chen G, et al. Acta Cryst., 2001,C57:349-351[22] Cui Y, Chen J, Chen G, et al. Acta Cryst., 2001,C57:349-351
23. [23] Siemeling U, Vorfeld U, Neumann B, et al. Chem. Commun., 1997:1723-1724[23] Siemeling U, Vorfeld U, Neumann B, et al. Chem. Commun., 1997:1723-1724
24. [24] Botana L, Ruiz J, Seco J M, et al. Dalton Trans., 2011,40:12462-12471[24] Botana L, Ruiz J, Seco J M, et al. Dalton Trans., 2011,40:12462-12471
25. [25] Song Y F, van Albada G A, Tang J, et al. Inorg. Chem., 2007,46:4944-4950[25] Song Y F, van Albada G A, Tang J, et al. Inorg. Chem., 2007,46:4944-4950
26. [26] Bu X H, Du M, Shang Z L, et al. Inorg. Chem., 2000,39:4190-4199[26] Bu X H, Du M, Shang Z L, et al. Inorg. Chem., 2000,39:4190-4199
27. [27] Du M, Zhao X J, Guo J H, et al. Eur. J. Inorg. Chem., 2005,294-304[27] Du M, Zhao X J, Guo J H, et al. Eur. J. Inorg. Chem., 2005,294-304
28. [28] Thomspson L K, Mandal S K, Tandon S S, et al. Inorg. Chem., 1996,35:3117-3125[28] Thomspson L K, Mandal S K, Tandon S S, et al. Inorg. Chem., 1996,35:3117-3125

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性

通讯作者: 寇会忠,E-mail:kouhz@mail.tsinghua.edu.cn

English

Synthesis, Structure and Magnetic Properties of Phenoxo-Bridged Polynuclear Cu(Ⅱ) Complexes

Corresponding author: 寇会忠,E-mail:kouhz@mail.tsinghua.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性

通讯作者: 寇会忠,E-mail:kouhz@mail.tsinghua.edu.cn

English

Synthesis, Structure and Magnetic Properties of Phenoxo-Bridged Polynuclear Cu(Ⅱ) Complexes

Corresponding author: 寇会忠,E-mail:kouhz@mail.tsinghua.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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