单一手性烯烃铜(Ⅰ)配位聚合物

Vol.23 No.72007年7月CHINESE JOURNAL OF INORGANIC CHEMISTRYJul, 2007行研究简报$公公公公司单一手性烯烃铜( |)配位聚合物庞洁王国喜熊仁根*(南京大学化学化工学院,配位化学研究所,配位化学国家重点实验室,南京210093)关键词:烯烃铜([);水热法;配位聚合物;晶体结构中图分类号: 0614.121文献标识码: A文章编号: 1001-4861(2007)07-1227-03A Homochiral Olefin-copper(I) Coordination PolymerPANG Jie WANG Guo-Xi XIONG Ren-Gen*(Coordination Chemistry Institue, State Key Laboratory of Coordination Chemistry, Nanjing Univrsity, Nanjing 210093)Abstract: The solvothermal reaction of CuCl with R-)-1-allyl-3- methylpiperazine at 70 C gives one-dimensionalchain Cu-coordination polymer through olefin moiety binding to Cu atoms formulated as [Cu (CgHcN2)C1]. It isinteresting to note that through Cu2Cl2 dimer unit 1 results in a supramolecular 3-dimensional coordination polymer.Powdered sample measurement of 1 reveals that 1 is second-harmonic generation (SHG) active compound. Crystalparameters for 1, space group P221, a=0.763 1(9) nm, b=0.891 0(10) nm, c=1.494 6(17) nm, a=90°, β=90°, γ=90°, V=1.016(2) nm', Z=2, M=478.44, D.=1.564 Mg. m~3. CCDC: 650193.Key words: olefin copper(1); solvothermal; coordination polymer; crystal structure0 Introductionligand with olefin moiety reacting with Cu(I) to form theolefin-Cu (I) coordination polymers is very rare andOlefin moiety coordination to copper(I) has foundremains largely unexplored. As a continuation of oura wide spread applications such as olefin derivativesolefin copper (I) coordination chemistry program, weseparation, bioinorganic chemistry, and purification COhave performed the following reaction as shown infor petroleum industry. On the other hand, the formationScheme 1. The produced olefin copper(I) coordinationof olefin-copper(I) coordination polymer stabilizes thepolymer (1) (Cu(CxHysN)Cl, copper chloride mono[R-(-)bond of olefin-Cu(I) so that many olefin-Cu(I) coor--1-allyl-3-methylpiperazine] displays a one dimension-dination polymers have been produced recently in myal infinite chain structural feature with ai 3-dimensionalgroup while they have found many practical utilizationssupramolecular structure through a pseudo-dimerlike SHG materials, ferroelectricity and fluorescent ma-Cu2Cl2 unit. Herein we report its synthesis and crystaltrialsl-T. Homochiral olefin copper coordinatin poly-mers reported in literatures show that there are only two70C(A")eccasesbased on natural product cinchona with olefin(1)moiety, as we are awareS5间. The synthesized homochiralScheme 1收稿日期:2007-04-02。收修改稿日期:2007-06-20。国家自然科学基金资助项目(No.NSF20471029)。*通讯联系人。Email:xiongrg@nju.edu.cn第-作者:庞洁,女,26岁,硕士研究生;研究方向:手性化合物的合成。1228无机化学学报第23卷.structure and preliminary SHG measurement.dimer Cu2Cl2 unit to result in the pseudo-three-dimensional coordination polymer, as depicted in Fig.3.1 Experimental.1 Materials and physical measurementsAll starting materials were of A.R. grade, obtainedfrom commercial suppliers and used without furtherpurification. The FTIR spectra were recorded as solidin KBr matrix in the range 4 000~400 cm-1 on VECTOR-22 FTIR spectrometer.:al1.2 Preparation of the Ligand (R-(-)-allyl-3-NIAmethylpiperazine)The R-(-)-3-methylpiperazine (0.6 mol) was react-ed with allyl bromide (0.2 mol) at 65 C in the solvent ofmethylbenzene to give the product (R-(-)-allyl-3-me-thylpiperazine). Yield: ca. 70.5% based on R-(-)-3-me-thylpiperazine. b.p.191 C.Fig.1 Asymmetric unit of Cu(CsHsN2)Cl (1) showing thatIR (KBr, cm-): 3 422.53(s), 2936.00(9), 2 804.19the local coordination environment around Cu(s), 1 642.48(m), 1 457.30(m), 1 376.08(w), 1 326.07(w),atom can be best descibed as linearly trigonal1 140.19(s), 1 054.40(w), 996.76(w), 919.15(m), 821.54mode composed of N atom, olefin moiety and a(w), 573.47(w).termal Cl atom .MS(m/e): (M+ 1) 141.20 (isotopic peak 142.23)1.3 Preparation of the [Cu(CH,N)CI] (1)Solvothermal treatment of CuCl (1 mmol), R-(-)-1-allyl-3-methylpiperazine (1 mmol) and methanol (2 mL)over 1 day at 70 9C yield a pale yellow prismaticcrystalline product. The yield of 1 was about 43%.IR (KBr, cm* ): 3453.25(w), 3148.38(s), 2934.64(s), 2 815.37(s), 2759.46(m), 1 526.80(w), 1 448.45(s),1 385.32 (w), 1 33.27 (w), 1 305.40 (w), 1 253.18(m),1 167.83 (m),1 135.49 (s), 1096.11 (m), 1012.08(), .983.1 1(s), 954.41(w), 900.22(w), 850.80(m), 800.15(m),Fig.2 One-dimensional infinite chain representation of4231(w).Cu(CgH&N)Cl2 Results and discussionUnder s olvothermal reaction conditions (Scheme1), the produced olefin copper coordination polymer, 1has a tri-coordinated linear central Cu atom as shown inFig.1 while the ligand [R-(-)-allyl-3-methylpiperaz-ine] acts as bidentate linker to bridge two Cu atomsthrough N atom and olefin moiety to result in theFig.3 A pseudo-thee-dimensional representation of Cuformation of one-dimensional Cu coordination polymer(CgHuN2)Cl through weak coordination Cl to(Fig.2). It is interesting to note that the terminal Cl atomanother Cu atom to resuling to the formation ofalso takes part in to another Cu atom through weaka weak Cu2Cl2 dime unit第7期庞洁等:单一手性烯烃铜()配位聚 合物1229To confirm its space group, the powdered samplemeasurement of SHG shows that 1 is active nonlinear[5] Xie Y R, Wang X S, Zhao H, et al. Orgunmeallics, 2003,22(2):4396- 4398optical materials about as the same as that of KDP.[6] Qu z R, Chen Z F, Zhang J. et al. Organomaeallics, 2003,22CCDC: 650193.(14):2814-2816[7](a)Xue X, Wang X s, Xiong R G, et al. Angew. Chem. Int. Ed.,References:2002,41(16):2944-2946(b)Zhang J, Xiong R G, Chen X T, et al. Organometallics, 2002,[1] HuangX F, SongY M, Wang X S, et al. J. Organomet. Chem,21(1):235-2382006,691(5):1065-1074(c)Zhang J, Xiong R G, Chen X T, et al. Organomeallics, 2001,[2} Wang X s, Zhao H, Li Y H, et al. Topics in Catalysis, 2005,3520(19):4118~4121(1~2):43-61(d)Zhang J, Xiong R C, ZuoJL, et al. J. Chem. 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