Citation: SUN Xiao-Mei, NING Wei-Hua, LIU Jian-Lan, LIU Shao-Xian, GUO Ping-Chun, REN Xiao-Ming. Three Dinuclear Cu+ Complexes Based on Cu₂X₂ Core (X^-=Cl^-, Br^- and I^-): Syntheses, Crystal Structures, Absorption and Emission Spectra[J]. Chinese Journal of Inorganic Chemistry, ;2013, 29(10): 2176-2182. doi: 10.3969/j.issn.1001-4861.2013.00.331 shu

Three Dinuclear Cu+ Complexes Based on Cu₂X₂ Core (X^-=Cl^-, Br^- and I^-): Syntheses, Crystal Structures, Absorption and Emission Spectra

1.
1 State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China;

Received Date: 31 March 2013
Available Online: 7 May 2013
Fund Project: 国家自然科学基金(No.21071080) (No.21071080)江苏省自然科学基金(No.BK2010551)资助项目 (No.BK2010551)

Three dinuclear Cu+ complexes [Cu₂(μ-X)₂(deebq)₂] (where deebq=4,4'-diethylester-2,2'-biquinoline; X=Cl (1), Br (2) or I (3)), have been synthesized and characterized spectroscopically. The isostructural 1～3 crystallize in triclinic system with space group Pl, and show quite similar lattice parameters and packing structures. Two Cu⁺ ions in a dinuclear unit are related to each other via an inversion center; each Cu⁺ ion are coordinated by two Natoms form one deebq ligand and two X^- anions, which act as a μ₂-bridge mode to link two Cu⁺ ions, to form a distorted tetrahedral coordination geometry. The dinuclear units are aligned into a supramolecular chain via the intermolecular π…π interactions between the neighboring phenyl rings in deebq ligands, and the supramolecular chains are held together through weakly intermolecular van der Waals forces. Three complexes exhibit a broad and asymmetric absorption band in the 500～630 nm range in CH₂Cl₂, this band is almost independent on the bridged X^- ligand and not observed in the absorption spectrum of deebq in CH₂Cl₂, thus, it is assigned to MLCTfrom Cu⁺ center to deebq ligand. Complexes 1～3 emitted intense fluorescence with the center around 400 nm, this emission band is attributed to the π-π^* electronic transition of deebq ligand. No MLCTemission was observed in the CH₂Cl₂ solution and the solid state for three complexes. CCDC: 888543, 1; 888542, 2; 888541, 3.
- 4,4'-diethylester-2,2'-biquinoline; dinuclear complex; crystal structure; MLCT; absorption spectra; emission spectra
1. [1]
  [1] Ruthkosky M, Kelly C A, Zaros M C, et al. J. Am. Chem. Soc., 1997,119:12004-12005 [2] Bignozzi C A, Argazzi R, Kleverlaan C, et al. J. Chem. Soc. Chem. Rev., 2000,29:87-96 [3] George B S, Christian D G, Hideaki S, et al. J. Am. Chem. Soc., 2007,129:2147-2160 [4] Thanasekaran P, Liao R T, Liu Y H, et al. Coord. Chem. Rev., 2005,249:1085-1110 [5] Vannelli T A, Karpishin T B. Inorg. Chem., 2000,39:1336- 1336 [6] Melinda H K, Kurt D B, Joseph T H, et al. Coord. Chem. Rev., 2000,205:201-228 [7] De S A P, Fox D B, Moody T S, et al. Pure Appl. Chem., 2001,73:503-511 [8] Rudzinski C M, Nocera D G. Mol. Supramol. Photochem., 2001,7:1-3 [9] Kapturkiewicz A. Electrochemistry of Functional Supramo- lecular Systems. Hoboken NJ: John Wiley & Sons, 2010:477 [10]Armaroli N, Balzani V, Barigelletti F, et al. J. Am. Chem. Soc., 1994,116:5211-5217 [11]Baldo M A, O'Brien D F, You Y, et al. Nature, 1998,395: 151-154 [12]Baldo M A, Thompson M E, Forrest S R, et al. Nature, 2000,403:750-753 [13]Collin J P, Dietrich-Buchecker C, Gavina P, et al. Acc. Chem. Res., 2001,34:477-487 [14]Sauvage J P. Science, 2001,291:2105-2106 [15]Li M Z, Bin L, Zhong M S, et al. J. Phys. Chem. C, 2009, 113:13968-13973 [16]Ali H, Van Lier J E. Chem. Rev., 1999,99:2379-2450 [17](a)Zhang Q S, Ding J Q, Cheng Y X, et al. Adv. Funct. Mater., 2007,17:2983-2990 (b)Moudam O, Kaeser A, Delavaux-Nicot B, et al. Chem. Commun., 2007,1:3077-3079 (c)Zhang Q S, Zhou Q G, Cheng Y X, et al. Adv. Funct. Mater., 2006,16:1203-1208 (d)Armaroli N, Accorsi G, Holler M, et al. Adv. Mater., 2006,18:1313-1316 (e)Zhang Q S, Zhou Q G, Cheng Y X, et al. Adv. Mater., 2004,16:432-436 [18](a)Kyle K R, Ryu C K, Dibenedetto J A, et al. J. Am. Chem. Soc., 1991,113:2954-2965 (b)Kim T H, Shin Y W, Jung J H, et al. Angew. Chem. Int. Ed., 2008,47:685-688 (c)Tran D, Bourassa J L, Ford P C, et al. Inorg. Chem., 1997,36:439-442 (d)Vitale, M, Ford P C. Coord. Chem. Rev., 2001,219:3-16 (e)De Angelis F, Fantacci S, Sgamellotti A, et al. Inorg. Chem., 2006,45:10576-10584 [19]Makowska-Janusik M, Gondek E, Kityk I V, et al. Chem. Phys., 2004,306:265-271 [20]Hoertz P G, Staniszewski A, Marton A, et al. J. Am. Chem. Soc., 2006,128:8234-8245 [21]Bruker, SAINT (Version 6.22) and SMART (Version 5.625), Bruker AXS Inc., Madison, WI, USA, 2001. [22]Sheldrick G M. SHELXL-97, Program for the Refinement of Crystal Structure; University of G?觟ttingen, G?觟ttingen, Germany, 1997. [23]Butcher R J, Sinn E. Inorg. Chem., 1977,16:2334-2343 [24]Sinn E. J. Chem. Soc. Dalton Trans., 1976,7:162-165 [25]Vatsadze S Z, Dolganov A V, Yakimanskii A V, et al. Russ. Chem. Bull. Int. Ed., 2010,4:710-718 [26]Ye J W, Zhang P, Ye K Q, et al. J. Solid State Chem., 2006,179:438-449 [27]Jahng Y, Hazelrigg J, Kimball D, et al. Inorg. Chem., 1997, 36:5390-5395 [28]Ali B F, Al-Sou'od K, Al-Ja'ar N, et al. J. Coord. Chem., 2006,59:229-241 [29]Shi X, Zhu G, Wang X, et al. Cryst. Growth Des., 2005,5: 341-346 [30]Wang X L, Qin C, Wang E, et al. Inorg. Chem., 2004,43: 1850-1856 [31]Shan X C, Jiang F L, Yuan D Q, et al. Dalton Trans., 2012, 41:411-416 [32]Chen X L, Wang J J, Hu H M, et al. Z. Anorg. Allg. Chem., 2007,633:2053-2058
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Three Dinuclear Cu+ Complexes Based on Cu2X2 Core (X-=Cl-, Br- and I-): Syntheses, Crystal Structures, Absorption and Emission Spectra

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通讯作者: 陈斌, bchen63@163.com

Three Dinuclear Cu+ Complexes Based on Cu₂X₂ Core (X^-=Cl^-, Br^- and I^-): Syntheses, Crystal Structures, Absorption and Emission Spectra