Citation: CUI Hong-Xia, YU Chu-Nan, CHEN Yan-Hong, JIANG Xiu-Yan, GAO Li, LIU Huan-Rong. Halogen Mediated Self-assembly of Three Mixed Valent Cu(I)/Cu(II) Complexes[J]. Chinese Journal of Structural Chemistry, ;2016, 35(1): 150-156. doi: 10.14102/j.cnki.0254-5861.2011-0791 shu

Halogen Mediated Self-assembly of Three Mixed Valent Cu(I)/Cu(II) Complexes

1.
School of Chemical Engineering, Shengli College China University of Petroleum, Dongying 257097, China

Received Date: 4 May 2015
Available Online: 11 September 2015
Fund Project:

Reaction of the ligand dmpt (dmpt = 6,7-dimethylbenzo[f][1,10]phenanthroline) with CuCl₂ afforded mixed valent Cu(I)/Cu(II) discrete tetranuclear complexes [Cu(II)Cl₂(dmpt)Cu(I)Cl] (1), while the reaction of ligand dppz (dppz = dipyrido[3,2-a:20,30-c] phenazine) with divalent halogen copper salt CuX₂(X = Cl, Br) gave one-dimensional chain mixed valent Cu(I)/Cu(II) complexes [Cu(II)Cl₂(dppz)Cu(I)Cl]_n (2) and discrete mixed valent Cu(I)/Cu(II) complexes [Cu(II)Br₂(dppz)(DMF)Cu(I)Br] (3). Complex 2 consists of a one-dimensional chain -dppzCu(II)-Clμ₂-Cu(I)-Cl-dppzCu(II)-Clμ₂-Cu(I)- with Cu(II) and Cu(I) atoms linked together by chloride anion. Complex 3 is a discrete complex, which is the same as complexes 1 and 2 involving two different copper valent Cu(I) and Cu(II). The Cu(I) ion presents a pseudo-trihedral geometry, while the Cu(II) ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover, halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.
- anion of halogen mediated self-assembly,
- mixed valence Cu(I)/Cu(II) complexes
1. [1]
  (1) Cook, T. R.; Zheng, Y. R.; Stang, P. J. Metal-organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal-organic materials. Chem. Rev. 2013, 113, 734-777.
2. [2]
  (2) Konar, S.; Zoń, J.; Prosvirin, A. V.; Dunbar. K. R.; Clearfield, A. Synthesis and characterization of four metal-organophosphonates with one-, two-,and three-dimensional structures. Inorg. Chem. 2007, 46, 5229-5236.
3. [3]
  (3) Wang, J. J.; Gou, L.; Hu, H. M.; Han, Z. X.; Li, D. S.; Xue, G. L.; Yang, M. L.; Shi, Q. Z. Ligand and pH-controlled Zn^II bilayer coordination colymers cased on biphenyl-3,3',4,4'-tetracarboxylate. Cryst. Growth Des. 2007, 7, 1514-1521.
4. [4]
  (4) Wu, S. T.; Long, L. S.; Huang, R. B.; Zheng, L. S. pH-dependent assembly of supramolecular architectures from 0D to 2D networks. Cryst. Growth Des. 2007, 7, 1746-1752.
5. [5]
  (5) Zhang, J.; Zhao, Y.; Gamboa, S. A.; Lachgar, A. Metal-ligand directed assembly of layered cluster-based coordination polymer and its solvent-mediated structural transformations. Cryst. Growth Des. 2008, 8, 172-175.
6. [6]
  (6) Chen, J.; Wang, J.; Ulrich, J.; Yin, Q.; Xue, L. Effect of solvent on the crystal structure and habit of hydrocortisone. Cryst. Growth Des. 2008, 8, 1490-1494.
7. [7]
  (7) Wang, C. J.; Ma, H. R.; Wang, Y. Y.; Liu, P.; Zhou, L. J.; Shi, Q. Z.; Peng, S. M. Subtle structural changes in coordination chains: influence of the flexibility of theprecursor ligands and of the solvent. Cryst. Growth Des. 2007, 7, 1811-1817.
8. [8]
  (8) Chen, G. J.; Gao, F. X.; Huang, F. P.; Tian, J. L.; Gu, W.; Liu, X.; Yan, S. P.; Liao, D. Z. Sodium-mediated self-assembly: three novel 2D coordination aggregates of 1,4,7-triazacyclononane-N,N',N''-tripropionate. Cryst. Growth Des. 2009, 6, 2662-2667.
9. [9]
  (9) Maiti, B. K.; Pal, K.; Sarkar, S. Plasticity in [(R₄-xR1x)₄N]₄[Cu₄{S₂C₂(CN)₂}₄] (x = 0～4) is molded by a guest cation on an elastic anionic host. Eur. J. Inorg. Chem. 2008, 2407-2420.
10. [10]
  (10) Ma, J. P.; Dong, Y. B.; Huang, R. Q.; Smith, M. D.; Su, C. Y. Spontaneously resolved chiral three-fold interpenetrating diamondoidlike Cu(II) coordination polymers with temperature-driven crystal-to-crystal transformation. Inorg. Chem. 2005, 44, 6143-6145.
11. [11]
  (11) Kitamura, M.; Hironaka, S. Effect of temperature on antisolvent crystallization and transformation behaviors of thiazole-derivative polymorphs. Cryst. Growth Des. 2006, 6, 1214-1218.
12. [12]
  (12) Wang, J. P.; Bi, D. Q.; Niu, J. Y. A three-dimensional heterocluster containing manganese clusters and hexanuclear sodium wheels. CrystEngComm. 2007, 9, 740-742.
13. [13]
  (13) Vitale, M.; Ford, P. C. Luminescent mixed ligand copper(I) clusters (CuI)_n(L)_m (L = pyridine, piperidine): thermodynamic control of molecular and supramolecular species. Coord. Chem. Rev. 2001, 219, 3-16.
14. [14]
  (14) Ford, P. C.; Vogler, A. Photochemical and photophysical properties of tetranuclear and hexanuclear clusters of metals with d¹⁰ and s² electronic configurations. Acc. Chem. Res. 1993, 26, 220-226.
15. [15]
  (15) Lu, J. Y.; Cabrera, B. R.; Wang, R. J.; Li, J. Chemical rearrangement under hydrothermal conditions: formation of polymeric chains (CuX)₂(dpiz) and (CuX)₃(dpiz) (X = Cl, Br; dpiz = dipyrido[1,2-a:2',3'-d]imidazole) and crystal structures of [(CuCl)₂(C₁₀H₇N₃)] and [(CuBr)₃(C₁₀H₇N₃)]. Inorg. Chem. 1998, 37, 4480-4481.
16. [16]
  (16) Lu, J. Y.; Cabrera, B. R.; Wang, R. J.; Li, J. Cu-X-bpy (X = Cl, Br; bpy = 4,4'-bipyridine). Coordination polymers: the stoichiometric control and structural relations of [Cu₂X₂(bpy)] and [CuBr(bpy)]. Inorg. Chem. 1999, 38, 4608-4611.
17. [17]
  (17) Hoskins, B. F.; Robson, R. Design and construction of a new class of scaffolding-like materials comprising infinite polymeric frameworks of 3D-linked molecular rods. A reappraisal of the zinc cyanide and cadmium cyanide structures and the synthesis and structure of the diamond-related frameworks [N(CH₃)₄][CuIZnII(CN)₄] and CuI[4,4',4'',4'''-tetracyanotetraphenylmethane]BF₄.xC₆H₅NO₂. J. Am. Chem. Soc. 1990, 112, 1546-1554.
18. [18]
  (18) Pohl, A. H.; Chippindale, A. M.; Hibble, S. J. New copper(I) cyanide networks: interpenetration, self-penetration and polymorphism. Solid State Sci. 2006, 8, 379-387.
19. [19]
  (19) Inoue, M. B.; Inoue, M.; Machi, L.; Brown, F.; Fernando, Q. Charge-transfer complexes of benzylviologen (1,1'-dibenzyl-4,4'-bipyridinium(2+) cation) with cyanocuprate(I) and the structure of (BzV)₃Cu₉(CN)₁₅·H₂O. Inorg. Chim. Act. 1995, 230, 145-151.
20. [20]
  (20) Yun, S. S.; Moon, H. S.; Kim, C. H.; Lee. S. G. A novel, wave-like, two-dimensional anionic host with cationic and neutral guests: crystal structure of [C₆H₁₁NH₃][Cu₂(CN)₃]₂C₆H₅NH₂. J. Coord. Chem. 2004, 57, 321-327.
21. [21]
  (21) Liu, S.; Meyers, E. A.; Shore, S. G. An inclusion complex with [Gd(dmf)₈]³⁺ ions encapsulated in pockets of an anionic array of [{Cu₆(CN)₉}^3-] units; a cyanide-bridged Cu-Gdlayer structure. Angew. Chem., Int. Ed. 2002, 41, 3609-3611.
22. [22]
  (22) Liu, S.; Plecnik, C. E.; Meyers, E. A.; Shore, S. G. Two distinct Ln(III)-Cu(I) cyanide extended arrays: structures and synthetic methodology for inclusion and layer complexes. Inorg. Chem. 2005, 44, 282-292.
23. [23]
  (23) Khan, N. A.; Baber, N.; Iqbal M. Z.; Mazhar, M. Mechanism of decomposition of cuprous cyanide. Infrared and thermal evidence. Chem. Mater. 1993, 5, 1283-1286.
24. [24]
  (24) Krause, N.; Gerold, A. Regio- and stereoselective syntheses with organocopper reagents. Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204.
25. [25]
  (25) Chan, Z. K.; Lin, C. H.; Wang, C. C.; Chen, J. D.; Wang, J. C.; Liu, C. W. Syntheses, structures and magnetism of linear tri- and tetra-copper chains containing anions of N,N'-bis(pyrimidine-2-yl)formamidine. Dalton Trans. 2008, 16, 2183-2189.
26. [26]
  (26) Ziad, D.; Cisnetti, F.; Dupont, L.; Henon, E.; Policar, C.; Guillon, E. Synthesis, characterization and dioxygen reactivity of copper(I) complexes witgly coligands. Dalton Trans. 2008, 24, 3235-3245.
27. [27]
  (27) Hao, H. Q.; Wang, J.; Liu, W. T.; Tong, M. L. Two 3D hybrid networks of mog and bcu topology constructed with copper(I/I,II) halides and N,N'-spacers. CrystEngComm. 2008, 10, 1454-1459.
28. [28]
  (28) Li, W.; Li, M. X.; Shao, M.; Wang, Z. X.; Liu, H. J. Ferromagnetic and mixed-valence copper coordination polymers assembled by polycarboxylates and 2,6-bis(1,2,4-triazolyl)pyridine. Inorg. Chem. Comm. 2008, 11, 954-957.
29. [29]
  (29) Smolenski, P.; Kłak, J.; Nesterov, D. S.; Kirillov, A. M. Unique mixed-valence Cu(I)/Cu(II) coordination polymer with new topology of bitubular 1D chains driven by 1,3,5-triaza-7-phosphaadamantane (PTA). Cryst. Growth Des. 2012, 12, 5852-5857.
30. [30]
  (30) Chen, G. J.; Wang, Z. G.; Qiao, X.; Xu, J. Y.; Tian, J. L.; Yan, S. P. Synthesis, DNA binding, photo-induced DNA cleavage, cytotoxicity studies of a family of heavy rare earth complexes. Journal of Inorganic Biochemistry 2013, 127, 39-45.
31. [31]
  (31) Chen, G. J.; Qiao, X.; Qiao, P. Q.; Xu, G. J.; Xu, J. Y.; Tian, J. L.; Gu, W.; Liu, X.; Yan, S. P. Synthesis, DNA binding, photo-induced DNA cleavage, cytotoxicity and apoptosis studies of copper(II) complexes. J. of Inorg. Biochem. 2011, 105, 119-126.
32. [32]
  (32) Sheldrick, G. M. SHELXS 97, Program for the Solution of Crystal Structures. University of Götingen, Germany 1997.
33. [33]
  (33) Sheldrick, G. M. SHELXL 97, Program for the Refinement of Crystal Structures. University of Götingen: Germany 1997.
34. [34]
  (34) Shields, G. P.; Raithby, P. R.; Allena, F. H.; Motherwell, W. D. S. The assignment and validation of metal oxidation states in the Cambridge structural database. Acta Cryst. B 2000, 56, 455-465.
35. [35]
  (35) Levi, E.; Aurbacha, D.; Isnard, O. Bond-valence model for metal cluster compounds. I. Common lattice strains. Acta Cryst., B 2013, 69, 419-425.
36. [36]
  (36) Palenik, G. J. Bond valence sums in coordination chemistry using oxidation state independent R₀ values. A simple calculation of the oxidation state of titanium in complexes containing Ti-N, Ti-O, and Ti-Cl bonds. Inorg. Chem. 1997, 36, 3394-3397.
37. [37]
  (37) Palenik, G. J. Bond valence sums in coordination chemistry using oxidation state independent R₀values. Inorg. Chem. 1997, 36, 122-122.
38. [38]
  (38) Mclachlan, G. A.; Fallon, G. D.; Martin, R. L.; Spiccia, L. Synthesis, structure and properties of five-coordinate copper(II) complexes of pentadentate ligands with pyridyl pendant arms. Inorg. Chem. 1995, 34, 254-261.
39. [39]
  (39) Akhriff, Y.; Server-Carrió, J.; Sancho, A.; García-Lozano, J.; Escrivá, E.; Folgado, J. V.; Soto, L. Synthesis, crystal structure, and magnetic properties of oxalate-copper(II) complexes with 3,3-bis(2-imidazolyl)propionic acid, an imidazole-carboxylate polyfunctional ligand: from mononuclear entities to ladder-like chains. Inorg. Chem. 1999, 38, 1174-1185.
40. [40]
  (40) Akhriff, Y.; Server-Carrió, J.; Sancho, A.; García-Lozano, J.; Escrivá, E.; Soto, L. Two polymeric compounds built from mononuclear and tetrameric squarate-copper(II) complexes by the deprotonation of 3,3-bis(2-imidazolyl)propionic acid (HBIP). Synthesis, crystal structure, and magnetic characterization of [Cu(HBIP)(BIP)](C₄O₄)_1/2·2H₂O and [{Cu(BIP)(OH₂)}4(μ-C₄O₄)](ClO₄)₂·4H₂O. Inorg. Chem. 2001, 40, 6832-6840.
1. [1]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
2. [2]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
3. [3]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127
4. [4]
  Sifan Du , Yuan Wang , Fulin Wang , Tianyu Wang , Li Zhang , Minghua Liu . Evolution of hollow nanosphere to microtube in the self-assembly of chiral dansyl derivatives and inversed circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(7): 109256-. doi: 10.1016/j.cclet.2023.109256
5. [5]
  Cheng-Yan Wu , Yi-Nan Gao , Zi-Han Zhang , Rui Liu , Quan Tang , Zhong-Lin Lu . Enhancing self-assembly efficiency of macrocyclic compound into nanotubes by introducing double peptide linkages. Chinese Chemical Letters, 2024, 35(11): 109649-. doi: 10.1016/j.cclet.2024.109649
6. [6]
  Changlin Su , Wensheng Cai , Xueguang Shao . Water as a probe for the temperature-induced self-assembly transition of an amphiphilic copolymer. Chinese Chemical Letters, 2025, 36(4): 110095-. doi: 10.1016/j.cclet.2024.110095
7. [7]
  Yu Zhou , Lin-Tao Jiang , Xiao-Ming Jiang , Bin-Wen Liu , Guo-Cong Guo . Mixed-anion square-pyramid [SbS₃I₂] units causing strong second-harmonic generation intensity and large birefringence. Chinese Chemical Letters, 2025, 36(4): 109740-. doi: 10.1016/j.cclet.2024.109740
8. [8]
  Zengchao Guo , Weiwei Liu , Tengfei Liu , Jinpeng Wang , Hui Jiang , Xiaohui Liu , Yossi Weizmann , Xuemei Wang . Engineered exosome hybrid copper nanoscale antibiotics facilitate simultaneous self-assembly imaging and elimination of intracellular multidrug-resistant superbugs. Chinese Chemical Letters, 2024, 35(7): 109060-. doi: 10.1016/j.cclet.2023.109060
9. [9]
  Junyi Yu , Yin Cheng , Anhong Cai , Xianfeng Huang , Qingrui Zhang . Synthetic Cu(Ⅲ) from copper plating wastewater for onsite decomplexation of Cu(Ⅱ)- and Ni(Ⅱ)-organic complexes. Chinese Chemical Letters, 2025, 36(2): 110549-. doi: 10.1016/j.cclet.2024.110549
10. [10]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
11. [11]
  Bing Niu , Honggao Huang , Liwei Luo , Li Zhang , Jianbo Tan . Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chinese Chemical Letters, 2025, 36(2): 110431-. doi: 10.1016/j.cclet.2024.110431
12. [12]
  Yi Zhou , Wei Zhang , Rong Fu , Jiaxin Dong , Yuxuan Liu , Zihang Song , Han Han , Kang Cai . Self-assembly of two pairs of homochiral M₂L₄ coordination capsules with varied confined space using Tröger's base ligands. Chinese Chemical Letters, 2025, 36(2): 109865-. doi: 10.1016/j.cclet.2024.109865
13. [13]
  Gangsheng Li , Xiang Yuan , Fu Liu , Zhihua Liu , Xujie Wang , Yuanyuan Liu , Yanmin Chen , Tingting Wang , Yanan Yang , Peicheng Zhang . Three-step synthesis of flavanostilbenes with a 2-cyclohepten-1-one core by Cu-mediated [5 + 2] cycloaddition/decarboxylation cascade. Chinese Chemical Letters, 2025, 36(2): 109880-. doi: 10.1016/j.cclet.2024.109880
14. [14]
  Tao Yu , Vadim A. Soloshonok , Zhekai Xiao , Hong Liu , Jiang Wang . Probing the dynamic thermodynamic resolution and biological activity of Cu(Ⅱ) and Pd(Ⅱ) complexes with Schiff base ligand derived from proline. Chinese Chemical Letters, 2024, 35(4): 108901-. doi: 10.1016/j.cclet.2023.108901
15. [15]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
16. [16]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
17. [17]
  Jing JIN , Zhuming GUO , Zhiyin XIAO , Xiujuan JIANG , Yi HE , Xiaoming LIU . Tuning the stability and cytotoxicity of fac-[Fe(CO)₃I₃]^- anion by its counter ions: From aminiums to inorganic cations. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 991-1004. doi: 10.11862/CJIC.20230458
18. [18]
  Jiaxuan Wang , Tonghe Liu , Bingxiang Wang , Ziwei Li , Yuzhong Niu , Hou Chen , Ying Zhang . Synthesis of polyhydroxyl-capped PAMAM dendrimer/silica composites for the adsorption of aqueous Hg(II) and Ag(I). Chinese Chemical Letters, 2024, 35(12): 109900-. doi: 10.1016/j.cclet.2024.109900
19. [19]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
20. [20]
  Jumei Zhang , Ziheng Zhang , Gang Li , Hongjin Qiao , Hua Xie , Ling Jiang . Ligand-mediated reactivity in CO oxidation of yttrium-nickel monoxide carbonyl complexes. Chinese Chemical Letters, 2025, 36(2): 110278-. doi: 10.1016/j.cclet.2024.110278

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(821)
HTML views(41)

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