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配位聚合物[cu(niph)(bpy)]的合成,结构及性质Cu(niph)(bpy)即Copper(II) 聚萘酚(Bipyridyl)复配聚合物，是一种常
见的无机聚合物，具有扩展的六面体框架结构，以Cu2+离子为中心，
可以容纳18个氧化物离子或其他分子。
Cu(niph)(bpy) 复配聚合物的结构是以Cu2+为中心，可以容纳18个氧化物离子或其他分子，配位四
价萘酚（bipyridyl，简称bpy）大部分和分子有关，可以再氧化配位。
Bpy以草灰石配位形式存在，它是通过两个碳-氮键相连，它们呈面形
式把Cu2+离子八价包裹起来。
Cu(niph)(bpy) 复配聚合物主要用于离子交换、吸附、催化等应用，因
其富含配位基可以极大提高其离子交换性能。
由于Cu(niph)(bpy)复配
聚合物具有非常强的生物、环境友好的特性，因此可以用于容积分离、电化学催化、能量储存等多种应用。
例如，用于分离体外和体内的氢
离子，可在纳米结构中注入氢离子，然后在条件适宜的环境中控制它
们的相互作用，从而有效地分离和储存氢离子。
此外，Cu(niph)(bpy)复配聚合物也可作为类似生物膜的模板材料参与材料合成，用于分离、吸附和合成敏感分子，在这一方面具有前景。
近
年来，随着晶体学和材料学的不断发展，Cu(niph)(bpy) 复配聚合物的
研究也越来越受到人们的重视，在各种应用中得到越来越多的应用。
收稿日期：2009-12-07。
收修改稿日期：2010-04-14。
安徽省高校自然科学基金资助(No.KJ2009B104)，安徽省应用化学重点建设学科基金资助(No.200802187C)。
＊通讯联系人。
E -mail ：wugangczu@ 第一作者：吴刚，男，46岁，博士，副教授；研究方向：功能配合物。
＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊＊研究简报铜髤与2-吡啶酸、4，4′-联吡啶配合物的合成、结构和电化学性质吴刚＊,1王小锋2鲜华2郭学林1(1滁州学院化学和生命科学系，滁州239012)(2晓庄学院生物化工与化境工程学院，南京211171)关键词：Cu 髤配合物；4，4′-联吡啶；晶体结构；循环伏安中图分类号：O614.121文献标识码：A文章编号：1001-4861(2010)07-1315-04Synthesis,Crystal Structure and Cyclic Voltametric Property of Cu 髤Complex with 4,4′-Bipy and α-Pyridine CarboxylateWU Gang ＊,1WANG Xiao -Feng 2XIAN Hua 2GUO Xue -Lin 1(1Department of Chemistry and Life Science,Chuzhou University,Chuzhou,Anhui 239012)(2Biochemistry &Environment Engineering College,Xiao Zhuang University,Nanjing 211171)Abstract:The complex [Cu(bipy)(pc)(H 2O)(ClO 4)]·H 2O (1)(bipy:4,4′-bipyridine;Hpc:α-pyridine carboxylic acid)has been synthesized and characterized by single crystal X -ray diffraction method and elemental analysis.It crysrallizes in the Monoclinic space group P 21/n .The crystal structure reveals that Cu 髤centre adopts a pseudo octahedral geometry.Ligand 4,4′-bipyridine as a bridge coordinates to two different Cu 髤center to form a one -dimensional zigzag chain.One dimensional chains are linked by C-H …O hydrogen bonding interactions to form two -dimensional yers are connected by O …H-O hydrogen bond to generate three -dimensional structure.The cyclic voltametric behavior of complex 1is also DC:743537.Key words:copper 髤complex;4,4′-bipyridine;cyclic voltametryMetallo -supramolecular species built from transi -tion metal ions and organic ligands have been rapidly developed in recent years because of their fascinating structural diversities and potential applications in the areas of catalysis,gas storage,magnetism,nonlinear optics,electrical conductivity,and molecular recogni -tion [1-4].Over the past decades,there have been various examples of the metal -organic coordination frameworks obtained by using pyridyl -based bridging ligands,inclu -ding simple 2-connecting ligand like 4,4′-bipyridine [5-7].As a rigid linear bridging ligands,is often used in the design and constructure of multi -dimensional coordination polymers.It can connect metal cations through its distal pyridyl nitrogen donor atoms into structurally intriguing solids with potentially useful properties [8-12].For example,the paratactic layered phase [Zn (isophthalate)(4,4′-bpy)2][Zn (isophthalate)-(4,4′-bpy)]·0.25H 2O exhibits blue luminescence upon ultrav -iolet irradiation [13],and the interpenetrated 3D material [Zn(terephthalate)(4,4′-bpy)0.5]can chromatographically第26卷第7期2010年7月Vol ．26No ．71315-1318无机化学学报CHINESE JOURNAL OF INORGANIC CHEMISTRY第26卷无机化学学报separate branched and linear hydrocarbons[12].Here,a new4,4′-bipyridine coordination[Cu(bipy)(pc)(H2O) (ClO4)]·H2O is obtained and structure is determined by means of X-ray diffraction crystal structure analysis.Its cyclic voltametric property is investigated.1Experimental1.1Reagents and physical measurementsAll reagents commercially available were of reagent grade and used without further purification. Solvents were purified according to the standard methods.C,H and N elements analyses were carried out on a Perkin-Elmer240C elemental analyzer.IR spectra were recorded on a Vector22FTIR spectro-photometer by using KBr pellet in the range of4000~ 400cm-1.The electrochemical measurements were performed using a ShangHai ChenHua CHI600electro-chemical workstation.A three electrode platinum disc of2mm diameter,the reference electrode was Ag/AgCl electrode and single-compartment electrochemical cell was used.The working electrode was a platinum disc of 2mm diameter,the reference electrode was Ag/AgCl electrode and the counter electrode was a platinum wire long enough.All the measurements were carried out in N,N-dimethylformamide(DMF)solvent with0.1mol·L-1Bu4NPF6as indifferent electrolyte and all experi-ments were carried out at room temperature.The electrolyte solutions were carefully deaerated with dry N2.The bubbling was stopped during the measurements in order to obtain semi-infinite linear conditions for diffusion process of the electroactive specie complex with5mg·mL-1concentration.Voltammograms were recorded in the range from0.6to-0.8V vs Ag/AgCl and the scan rate was100mV·s-1.1.2Synthesis of the title compound(1)KOH(0.04mmol, 2.4mg)was added to the solution ofα-pyridine carboxylic acid(0.04mmol,5.0 mg)and4,4′-bipyrindine(bipy)(0.04mmol,5.0mg)in 5mL H2O.Then Cu(ClO4)2·6H2O(0.04mmol,14.8mg) and CH3CH2OH(7mL)were added with stirring.The clear solution was allowed to stand at ambient tempera-ture for about two weeks.Rod deep blue crystals were obtained(7.3mg).Anal.Calcd.for C16H14ClN3O8Cu(%): C,40.43;H,2.97;N,8.84.Found(%):C,40.38;H, 3.05;N,8.93.IR(KBr,cm-1):3450(bm),1636(s),1603 (s),1588(m),1570(w),1477(w),1405(w),1358(s),1293 (w),1217(w),991(m),807(w),810,771(w),696(w),612(w).1.3Crystal structure determinationThe crystal collection for complex1was carried out on a Bruker Smart ApexⅡCCD at room tempera-ture,using graphite-monochromated Mo Kαradiation (λ=0.07107nm).The structure was solved by direct methods and refined on F2by full-matrix least-squares techniques with SHELXL-97.All non-hydrogen atoms and hydrogen atoms were refined anisotropically and isotropically,respectively.The crystal parameters,data collection and refinement results for the compound are listed in Table1.The selected bond lengths and bond angles are listed in Table2.CCDC:743537.Table1Crystallographic data for complex1Empirical formula C16H16ClN3O8Cu D c/(g·cm-3) 1.65Formula weight477.32μ/mm-10.1326Crystal system Monoclinic Crystal dimension/mm0.24×0.22×0.20Space group P21/nθrange/(°) 1.93~26.00a/nm0.85357(8)F(000)972b/nm 1.61058(14)Goodness of fit 1.056c/nm 1.41685(13)Reflections collected10105β/(°)99.407(2)Independent reflns.(R int)3756(0.0203)V/nm3 1.9216(3)Obsd.reflns.(I>2σ(I))3345Z4Parameters refined262Temperature/K293(2)R,wR(I>2σ(I))0.0680,0.2069Crystal color Blue R,wR(all reflections)0.0724,0.2129 1316第7期吴刚等：铜髤与2-吡啶酸、4，4′-联吡啶配合物的合成、结构和电化学性质2Results and discussion2.1Crystal structure of the complex 1Complex 1crystallizes in the Monoclinic space group P 21/n .The coordination plot of the Cu 髤with the atomic numbering is shown in Fig.1.Each Cu 髤centre adopts a pseudo octahedral geometry with N 3O 3set.Three nitrogen atoms come from one α-pyridine carbox -ylate anion,which acts as a bidentate ligand chelating with Cu 髤center,and two bipy molecules,which acts as a bidentate ligand coordinating to two different Cu 髤center to generate a one -dimensional chain structure as ahown in Fig.2.In bipy molecule,two pyrindine rings are not in the same plane.The dihedral angle between two pyrindine rings is 21.99°.In addition,it is worthy to note that the O atom of perchlorate anion also partici -pate coordination with the metal atom since the distan -ces of Cu1-O4is 0.2790nm.Similar Cu -O distance of 0.2790nm has been reported in complex Ca[Cu(OAc)4]·6H 2O (OAc =acetate)[14].Selected bond lengths and angles for complex 1are listed in Table 2.The other two oxygen atoms are from ligands α-pyridine carboxy -late,water molecule,respectively.The heavily distorted octahedral geometry about Cu1is completed by loosely -bound perchlorate (O4,Cu -O is 0.2790nm)and water (O1W,0.23303(19)nm).The oxygen atoms from perc -hlorate and water molecule are localed at axial position.The angle of O4-Cu1-O1W is 175.23°.The [4+2]coor -dination is in line with that predicted for the Jahn -Teller active d 9ion Cu 2+.Bidentate ligand bipys bridge neighbour Cu 髤center to generate a zigzag one -dimensional chain (Fig.2).The [Cu(bipy)(pc)(H 2O)(ClO 4)]has an extensive capacity to hydrogen bonds through pc,coordinated water and perchlorate.Details of hydrogen bonds within 1are contained in Table 3.Firstly,the two dimensionalTable 2Selected bond lengths (nm)and angles (°)for complex 1Cu(1)-O(2)0.19444(14)Cu(1)-O(1W)0.23303(19)Cu(1)-N(2)#10.20186(16)Cu(1)-N(1)0.20072(16)Cu(1)-N(3)0.20065(16)Cu(1)-O(4)0.2790O(2)-Cu(1)-N(3)82.61(6)N(1)-Cu(1)-O(1W)91.86(7)N(3)-Cu(1)-O(1W)95.53(7)N(3)-Cu(1)-N(1)97.56(6)O(2)-Cu(1)-N(1)174.31(7)N(2)-Cu(1)-O(1W)#191.52(7)N(3)-Cu(1)-N(2)#1168.85(7)O(2)-Cu(1)-N(2)#188.34(6)O(2)-Cu(1)-O(1W)93.78(7)N(1)-Cu(1)-N(2)#190.80(6)Symmetry codes:#1:x -1/2,-y +1/2,z -1/2.Uncoordinated water molecule and hydrogen atoms omitted for clarityFig.1Coordination environment around the Cu 髤atom with 30%probability displacementSymmetry codes:#1:1-x ,-y ,-z ;#2:1+x ,-1+y ,z ;#3:x ,-1+y ,z ;#4:1/2-x ,1/2+y ,1/2-z ;#5:2-x ,1-y ,1-z ;#6:1/2+x ,-1/2-y ,1/2+z .D-H …Ad (D -H)/nm d (H …A)/nmd (D …A)/nm ∠(DHA)/(°)O(1W)-H(1WA)…O(2)#10.0960.2190.2795(4)120O(1W)-H(1WB)…O(6)#20.0960.1830.2739(17)157C(1)-H(1)…O(4)#30.0930.2550.3170(13)124C(2)-H(2)…O(1)#40.0930.2390.3316(5)173C(4)-H(4)…O(2W)#50.0930.2580.3445(10)155C(12)-H(12)…O(1)#60.0920.2320.3162(5)151Table 3Distance and angles of hydrogen bonds for the complex 11317第26卷无机化学学报nets are linked by C-H…O(C12-H12…O1#6)hydro-gen bond from uncoordinated oxygen atoms(acceptor)of pc anion and C-H(donor)of pc resulting in two dimensional layer(Fig.2).Further,O-H…O hydrogen bonding interactions between perchlorates with coordinated water moleules connects adjacent layers forming three-dimensional structure.2.2Cyclic voltammetric study of complex1Cyclic voltammetry between0.6to-0.8V permits the study of the complex1without decomposition.The sharp oxidation peak of copper is absent in this potential range(Fig.3).The oxidation peak of the complex occurs at about0.32V,and in the reverse scan it shows no obvious reduction peaks which indicates that the oxidation process of complex1is irreversible.References:[1]Leininger S,Olenyuk B,Stang P J.Chem.Rev.,2000,100:853-908[2]Westcott A,Fisher J,Harding L P,et al.J.Am.Chem.Soc.,2008,130:2950-2951[3]Coronado E,Galán-Mascarós J R,Gómez-García C J,et al.Nature,2000,408:447-449[4]Han F S,Higuchi M,Kurth D G.J.Am.Chem.Soc.,2008,130:2073-2081[5]Hagrman D,Hagrman P J,Zubieta J.Angew.Chem.Int.Ed.,1999,38:3165-3168[6]MacGillivray L R,Atwood J L.Angew.Chem.Int.Ed.,1999,38:1018-1033[7]Moulton B,Zaworotko M J.Chem.Rev.,2001,101:1629-1658[8]Lu W G,Su C Y,Lu T B,et al.J.Am.Chem.Soc.,2006,128:34-35[9]Qin C,Wang X L,Li Y G,et al.Dalton Trans.,2005:2609-2614[10]Zheng Y Q,Ying E R.Polyhedron,2005,24:397-406[11]Ghosh S K,Ribas J,Bharadwaj P K.Cryst.Growth Des.,2005,5:623-629[12]Chen B,Liang C,Yang J,et al.Angew.Chem.,Int.Ed.,2006,45:1390-1393[13]Dai Y M,Ma E,Tang E,et al.Cryst.Growth Des.,2005,5:1313-1315[14]Billing D E,Hathaway B J,Nivholls P.J.Chem.Soc.A,1970:1877-881Symmetry code:#6:1/2+x,-1/2-y,1/2+z;Perchlorate omitted for clarityFig.22D layer in1formed through hydrogen bonds indicated by dashed linesFig.3Cyclic voltammogram of complex1in DMF solution 1318。
2002年第60卷第12期,2167～2171化学学报ACT A CHI MICA SINICAV ol.60,2002N o.12,2167～2171五配位Cu(Ⅰ)配合物[Cu(4′2Phtpy)(PPh3)2](BF4)的合成、结构及光谱性质研究冯 巧a 李 丹ΞΞ,a 尹业高a 冯小龙b 蔡继文b(a汕头大学化学系 汕头515063)(b中山大学分析测试中心 化学与化工学院 广州510275)摘要 由[Cu(MeC N)2(PPh3)2](BF4)和4′2苯基22,2′:6′,2″2三联吡啶(4′2Phtpy)在室温下反应,合成了一个新颖的具有光致发光性能的五配位配合物[Cu(4′2Phtpy)(PPh3)2](BF4).对配合物进行了X射线衍射结构表征,并进行了红外光谱、紫外可见光谱、荧光光谱等光谱学分析.晶体属单斜晶系,空间群Pn,晶胞参数:a=110807(6)nm,b=110943(6)nm, c=211610(12)nm,α=90°,β=1021785(10)°,γ=90°,V=21492(2)nm3,Z=2,D c=11354g・cm-3.配合物中, Cu(Ⅰ)与4′2Phtpy的3个N,2个PPh3的P配位呈变形三角双锥型结构,其轴向由Cu键合联吡啶的末端2个N所组成,赤道平面由联吡啶的中心N原子和2个PPh3的P原子所组成.关键词 铜(Ⅰ)配合物,4′2苯基22,2′:6′,2″2三联吡啶,光致发光,晶体结构Synthesis,Structure and Spectroanalysis Studies ofa Five2coordinated Cu(Ⅰ)Complex[Cu(4′2Phtpy)(PPh3)2](BF4)FE NG,Qiao a LI,DanΞ,a YI N,Y e2G ao a FE NG,X iao2Long b C AI,Ji2Wen b(a Department o f Chemistry,Shantou Univer sity,Shantou515063)(b Instrumentation Analysis and Research Center,School o f Chemistry and Chemical Engineering,Zhongshan Univer sity,Guangzhou510275)Abstract A luminescence five2coordinated copper(Ⅰ)com plex of[Cu(4′2Phtpy)(PPh3)2](BF4)has been prepared by the reaction of[Cu(MeC N)2(PPh3)2](BF4)and4′2Phtpy(4′2Phtpy=4′2phenyl22,2′:6′,2″2 terpyridine)at room tem perature.The com plex was characterized with single crystal X2ray diffraction analysis, as well as IR,UV2vis abs orption and luminescence spectrometry.X2ray structural data show that the crystal belongs to m onoclinic system,and Pn space group with cell parameters a=110807(6)nm,b=110943(6) nm,c=211610(12)nm,α=90°,β=1021785(10)°,γ=90°,V=21492(2)nm3,Z=2,D c=11354 g・cm-3.The copper(Ⅰ)ion in the com plex has a distorted trig onal bipyramidal geometry,with the metal atom coordinated by tw o nitrogen atoms from the distal terpyridine pyridyl rings in axial sites.The equatorial plane is defined by the binding of nitrogen atom from the central pyridyl and tw o phosphorus atoms from PPh3. K eyw ords copper(Ⅰ)com plex,4′2phenyl22,2′:6′,2″2terpyridine,photoluminescence,crystal structure 具有光致发光性质的Cu(Ⅰ)的设计和合成一直是配位化学活跃的研究领域[1].多联吡啶化合物是一类具有特殊性质的配体,由于其多齿的配位点和对大多数金属离子的较强亲和力而备受关注[2],ΞE2mail:dli@Received July9,2002;accepted September19,2002.国家自然科学基金(N o.29901004),广东省自然科学基金(N o.000779)和汕头大学“211工程"学科建设基金资助项目1它们形成配位化合物的自组装作用和特殊的空间排列为拓扑化学和金属超分子化学提供了许多典型范例.2,2′:6′,2″2三联吡啶(terpy)是这类体系的重要成员之一,许多科学家致力于其与过渡金属配合物的光化学、电化学性质方面的研究[3,4].我们对Cu(Ⅰ)与膦、杂氮化合物形成的配合物的合成、结构和光致发光性能进行广泛的研究[5～9]. Cu(Ⅰ)主要形成四配位的配合物,也有一定数量的二、三配位,但五配位的Cu(Ⅰ)配合物则较为罕见[10].本文报道由4′2苯基22,2′:6′,2″三联吡啶(4′2 Phtpy)和三苯基膦(PPh3)与Cu(Ⅰ)形成的五配位混配配合物的合成、结构和光致发光性质的研究.1 实验部分1.1 试剂和仪器22乙酰吡啶、苯甲醛、三苯基膦等以及合成所用的其他试剂、溶剂均为市售商品,使用前不需进一步提纯.配体4′2苯基22,2′:6′,2″2三联吡啶(4′2 Phtpy)[11]和初始配合物[Cu(CH3C N)2(PPh3)2] (BF4)[12]按文献方法制备.红外和紫外吸收光谱分别在Nicolet Magna750 IR光谱仪(K Br压片)和岛津UV22501UV2vis分光光度计上记录.发射光谱在Perkin E lmer LS255荧光光谱仪获得,元素分析在Perkin E lmer240C元素分析仪测得,单晶衍射结构测定在Brucker S MART CC D 衍射仪上完成.1.2 配合物合成向[Cu(MeC N)2(PPh3)2](BF4)(1mm ol,017760 g)的V(二氯甲烷)∶V(甲醇)=1∶1混合溶液中,加入4′2Phtpy(013117g,1mm ol),溶液立刻变桔黄色(澄清).搅拌3h,过滤后将滤液用乙醚扩散,两天后析出方形桔红色晶体.IR(K Br压片)ν:3048w, 1609m(4′2Phtpy);1480m,1445s,1086vs,748m, 697s,523m(PPh3);1060s(BF4-)cm-1.Anal.calcd for C58H49BCuF4N3OP2:C72198,H5119,N4140; found C72111,H4192,N4154.1.3 晶体结构测定选用晶体大小0135mm×0145mm×0150mm,使用石墨单色化M o Kα(λ=01071073nm)辐射为光源,在温度293(2)K下,共收集独立衍射点14250个,其中I>2σ(I)的可观察衍射点7583个,强度数据经L P因子校正.晶体结构参数:[Cu(4′2Phtpy)(PPh3)2](BF4)・CH3OH,C58H49BCuF4N3OP2,M r=1016129,单斜晶系,空间群Pn,a=110807(6)nm,b=110943(6) nm,c=211610(12)nm,α=90°,β=1021785(10)°,γ=90°,V=21492(2)nm3;Z=2;Dc=11354 g1cm-3.晶体结构由直接法(SHE LXT L)解出,全部非氢原子坐标和温度因子经全矩阵最小二乘法修正,最终可靠因子R1=010513,wR2=011268.配合物的非氢原子坐标和等效热参数见表1.主要化学键键长、键角见表2.配合物的晶体数据已存于剑桥晶体数据中心(CC DC193812)以备免费索取[13],需要者也可向作者直接索取.2 结果与讨论2.1 配合物的晶体结构配合物的晶体结构分析表明,配合物由阳离子[Cu(4′2Phtpy)(PPh3)2]+和阴离子BF4-以及一个CH3OH溶剂分子成,阳离子[Cu(4′2Phtpy)2 (PPh3)2]+的结构见图1,阴离子BF4-未参加配位, CH3OH分子则无规则地分布在晶胞中.在[Cu(4′2 Phtpy)(PPh3)2]+中,Cu(Ⅰ)成五配位与4′2Phtpy的3个N,2个PPh3的P配位呈变形三角双锥型结构,其轴向由Cu键合联吡啶的末端2个N所组成,赤道平面由联吡啶的中心N原子和2个PPh3的P原子所组成.在赤道平面上,Cu(Ⅰ)和三联吡啶中心吡啶环上N(2)的键长为012120(4)nm,在常见的Cu—N键长范围[011999(9)～012161(13)nm]内,Cu和P(1), P(2)的键长分别为012302(2)nm和012298(2)nm,也与一般的Cu—P键长范围相近[012246(3)～012295(3)nm][10,14～16].轴向位置Cu(Ⅰ)与三联吡啶末端2个吡啶环上N的键长[Cu—N(1)012478(5), Cu—N(3)012501(5)nm]明显超出正常的Cu—N范围.说明赤道平面上N(2)与Cu(Ⅰ)的键合能力要比轴向N(1),N(3)的强,在Cu(Ⅱ)2三联吡啶配合物中也有类似的报道[17,18].赤道平面上对着Cu的夹角分别为N(2)—Cu(1)—P(1)=115199(11)°,N(2)—Cu(1)—P(2)= 119133(11)°,P(2)—Cu(1)—P(1)=124168(5)°,都与120°的理想值有偏离,其中以P—Cu—P夹角最大,可能是由于配体PPh3中苯环的空间结构拥挤所致.有趣的是,配体4′2Phtpy在配位前后结构发生很大变化.自由配体4′2Phtpy存在一个经过N(2),C(8), C(9),C(12)的二重轴,3个吡啶环关于环间碳-碳键8612 化学学报V ol.60,2002表1 标题配合物的非氢原子坐标参数(×104)和等效热参数(×105nm 2)T ab le 1 N on 2hydrogen atom ic coordinates (×104)and equivalent is otropicdis placement parameters (×105nm 2)x y z U (eq )x y z U (eq )Cu (1)-4730(1)-9224(1)-2525(1)54(1)C (28)-2786(6)-11871(6)-4492(3)62(2)P (1)-2707(1)-8844(1)-1948(1)41(1)C (29)-2346(5)-11181(6)-3953(3)64(2)P (2)-5343(1)-10971(1)-3103(1)40(1)C (30)-3112(5)-10931(5)-3545(3)52(1)B (1)-6870(9)-5141(12)-204(5)90(3)C (31)-5247(5)-12398(5)-2638(3)54(1)F (1)-8022(7)-5508(11)-360(5)243(6)C (32)-4333(6)-13257(5)-2652(3)66(2)F (2)-6295(13)-5746(18)-540(7)314(9)C (33)-4198(8)-14254(6)-2234(4)89(3)F (3)-6418(9)-5351(8)394(3)189(4)C (34)-5008(10)-14362(8)-1821(4)97(3)F (4)-6727(12)-4024(10)-379(5)235(6)C (35)-5893(9)-13496(8)-1811(3)90(3)C (1)-2443(4)-7490(5)-1439(2)45(1)C (36)-6052(6)-12500(6)-2217(3)69(2)C (2)-1402(5)-6743(5)-1358(3)56(1)C (37)-4028(5)-7894(5)-3876(3)59(1)C (3)-1187(6)-5821(5)-910(3)65(2)C (38)-3818(5)-6879(6)-4212(3)58(1)C (4)-2068(6)-5631(6)-544(3)66(2)C (39)-4417(7)-5816(6)-4122(3)66(2)C (5)-3127(7)-6359(6)-615(3)70(2)C (40)-5220(6)-5820(5)-3706(3)62(2)C (6)-3326(5)-7264(5)-1069(3)59(1)C (41)-5395(4)-6878(4)-3386(2)42(1)C (7)-2106(4)-10041(5)-1371(2)43(1)C (42)-6240(4)-6924(4)-2934(2)40(1)C (8)-2514(5)-11230(5)-1504(3)52(1)C (43)-7166(5)-6039(4)-2949(3)46(1)C (9)-2062(6)-12164(5)-1085(3)61(2)C (44)-7899(4)-6009(4)-2500(3)48(1)C (10)-1216(6)-11914(6)-533(3)67(2)C (45)-7687(5)-6933(5)-2048(3)49(1)C (11)-801(7)-10758(6)-387(3)75(2)C (46)-6817(4)-7850(4)-2073(2)40(1)C (12)-1246(6)-9815(5)-800(3)61(2)C (47)-6650(4)-8882(4)-1620(2)42(1)C (13)-1455(5)-8738(5)-2392(3)50(1)C (48)-7548(6)-9158(6)-1269(3)67(2)C (14)-549(5)-9631(6)-2382(3)65(2)C (49)-7366(6)-10103(7)-859(3)71(2)C (15)282(7)-9576(8)-2788(4)84(2)C (50)-6283(6)-10818(6)-796(3)64(2)C (16)217(8)-8635(10)-3204(4)91(3)C (51)-5457(6)-10502(5)-1159(3)60(2)C (17)-666(8)-7718(9)-3228(3)88(2)C (52)-8863(5)-5048(5)-2496(3)52(1)C (18)-1500(6)-7771(7)-2820(3)65(2)C (53)-9624(6)-4626(5)-3067(3)61(1)C (19)-6938(5)-11035(5)-3622(3)45(1)C (54)-10522(7)-3742(6)-3062(4)77(2)C (20)-7310(5)-10062(5)-4016(3)58(1)C (55)-10655(7)-3234(7)-2502(4)82(2)C (21)-8430(6)-10111(7)-4478(4)74(2)C (56)-9916(7)-3633(6)-1941(4)77(2)C (22)-9177(5)-11114(6)-4541(3)66(2)C (57)-9021(6)-4542(6)-1938(3)65(2)C (23)-8849(6)-12059(7)-4141(3)73(2)C (58)-4050(20)-3122(13)-9748(15)296(18)C (24)-7732(5)-12029(6)-3679(3)61(2)N (1)-4788(4)-7911(4)-3465(2)50(1)C (25)-4375(4)-11318(5)-3678(2)45(1)N (2)-6087(3)-7833(3)-2507(2)41(1)C (26)-4818(5)-11980(5)-4223(3)53(1)N (3)-5626(4)-9582(4)-1568(2)54(1)C (27)-4035(6)-12268(6)-4625(3)62(2)O (1)-3676(12)-4030(20)-9517(6)306(12) U (eq )is de fined as one third of the trace of the orth og onalized U ij tens or 1表2 [Cu (4′-Phtpy )(PPh 3)2](BF 4)・CH 3OH 的部分键长(nm )和键角(°)T ab le 2 S elected b ond lengths (nm )and angles (°)for [Cu (4′2Phtpy )(PPh 3)2](BF 4)・CH 3OH Cu (1)—P (1)0123022(17)Cu (1)—P (2)0122984(16)Cu (1)—N (1)012478(5)Cu (1)—N (2)012120(4)Cu (1)—N (3)012501(5)P (1)—Cu (1)—P (2)124168(5)P (1)—Cu (1)—N (1)100183(11)P (1)—Cu (1)—N (2)115199(11)P (2)—Cu (1)—N (2)119133(11)P (1)—Cu (1)—N (3)94130(12)P (2)—Cu (1)—N (3)101160(12)P (2)—Cu (1)—N (1)94190(12)N (1)—Cu (1)—N (2)72195(15)N (1)—Cu (1)—N (3)145157(13)N (2)—Cu (1)—N (3)72162(15)Cu (1)—N (1)—C (41)10810(3)Cu (1)—N (1)—C (37)13012(3)Cu (1)—N (2)—C (42)12010(3)Cu (1)—N (2)—C (46)12110(3)Cu (1)—N (3)—C (51)13015(4)Cu (1)—N (3)—C (47)10719(3)9612N o.12冯 巧等:五配位Cu (Ⅰ)配合物[Cu (4′2Phtpy )(PPh 3)2](BF 4)的合成、结构及光谱性质研究 图1 [Cu(4′2Phtpy)(PPh3)2]+的结构图(PPh3上苯环略)Figure1 S tructure of[Cu(4′2Phtpy)(PPh3)2]+PPh3phenyl rings om itted成反式构型(见图式1所示)[19].在配合物中,由于C u(Ⅰ)的诱导作用,配体的吡啶环发生翻转,成顺式构型(见图1所示),Cu(Ⅰ)离子在配合物形成过程中起模板作用.配体配位前后能量的改变应该被配合物的晶体场分裂能抵消,这样才能保证配合物以稳定形式存在.自由配体三个吡啶环关于环间碳-碳键近似共面,两个末端吡啶环与中间的吡啶环成517°两面角.配合物中,由于配体要形成Cu—N(1)和Cu(Ⅰ)—N(3)键的缘故,配体的3个吡啶环不共面,两个末端吡啶环与中心吡啶环分别成2011°和1615°夹角,有较大的扭曲,但扭曲程度远小于配合物[Cu2 (terpy)(PPh3)2](BF4)[10](terpy=2,2′:6′,2″2三联吡啶),其相应的数值为2715°和3113°.而在Cu(Ⅱ)2三联吡啶配合物,如[Cu(terpy)(H2O)(C4O4)]・H2O, [Cu2(terpy)2(H2O)2C4O4](ClO4),[Cu(terpy)(H2O)2 (NC O)](NO3)和[Cu(terpy)(H2O)2(NC O)](PF6)中[20,21]环夹角在0165°～3129°的范围内,不共面情况并不明显.在自由配体的晶体结构中,苯环和中心吡啶环成1019°夹角,而形成配合物后,此角度增大到4011°,估计是由于三联吡啶构型的改变所引起的空间结构的变化.2.2 配合物的光谱性质自由配体4′2Phtpy和配合物的紫外可见吸收光谱如图2所示.在室温下,乙腈溶液中配合物在253 nm和273nm处出现强吸收,低能量的峰一直延至340nm左右.在自由配体4′2Phtpy的吸收光谱中, 260nm前后有一强吸收峰,也有较长的弱拖尾峰,它属于4′2Phtpy的π2π3跃迁吸收[4],而自由的PPh3在260nm左右有一个来自膦的孤对电子到苯环的反键空轨道跃迁的吸收峰[22],因此,配合物低能量和高能量部分的吸收峰分别来自配体4′2Phtpy和配体PPh3的吸收.图式1 配体4′2Phtpy的分子结构示意图Scheme1 I llustration of the structure of free ligand4′2Phtpy图2 室温下配合物和配体4′2Phtpy在光谱纯乙腈溶液中的紫外-可见光谱Figure2 UV2vis abs orption spectra of com plex and free ligand 4′2Phtpy in acetonitrile at room tem perature1—C om plex;2—free ligand图3 室温下配合物和配体4′2Phtpy在光谱纯乙腈溶液中的荧光发射光谱图(330nm激发)Figure3 Emission spectra of com plex and free ligand4′2Phtpy in acetonitrile at room tem perature(excited at330nm)1—C om plex;2—free ligand0712 化学学报V ol.60,2002图3为室温下配体4′2Phtpy和配合物[Cu(4′2 Phtpy)(PPh3)2](BF4)在光谱纯乙腈中的荧光发射光谱.330nm激发时,配体4′2Phtpy在360,700nm左右出现了2个发射峰,而配合物的发射光谱与配体非常相似,出现在360,710nm处,配合物的发射应归结为配体内部的电荷迁移.3 结论配体4′2Phtpy与Cu(Ⅰ)配位前后结构发生较大变化,Cu(Ⅰ)的空间结构决定着配体的结合方式,即对配体的构型转变起着模板作用.该五配位Cu(Ⅰ)配合物具有光致发光性能,其发射主要来自配体.R eferences and N otes1Y am,V.W.2W.;Lo,K.K.2W.Chem.Soc.Rev.1999, 28,323.2C onstable,E. 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C.;Raithby,P.R.Inorg.Chim.Acta1990,178,47.20S olans,X.;Aguiló,M.;G leizes,A.;Faus,J.;Julve, M.;Verdaguer,M.Inorg.Chem.1990,29,775.21R ojo,T.;C ortes,R.;Lezama,L.;Mesa,J.L.;Via,J.;Arriortua,M.I.Inorg.Chim.Acta1989,165,91.22K utal,C.Coord.Chem.Rev.1990,99,213.(A0207093 SHE N,H.)1712N o.12冯 巧等:五配位Cu(Ⅰ)配合物[Cu(4′2Phtpy)(PPh3)2](BF4)的合成、结构及光谱性质研究。
