第27卷第9期 2011年9月 无 机 化 学 学 报 Vo1.27 No.9 1847.185 1 CHINESE JOURNAL OF INORGANIC CHEMIS 1’RY 二苯乙醇酸铜配合物的合成、晶体结构、电化学和荧光性质 杨颖群 陈满生 陈志敏 李 薇 (衡阳师范学院化学与材料科学系,衡阳421008) 摘要:以二苯乙醇酸为配体合成了1个新的化合物[Cu(2,2'-bipy)(BAA)l[Cu(2,2'-bipy)(BAA)(H O)】2・(H2O)3(BAA=Z.苯乙醇酸阴离 子,2,2'-bipy=2、,2 .联吡啶)。该化合物晶体属三斜晶系,空间群P1,晶胞参数:a=1.121 7(5)nm,6=1.3602(6)nm,c=2.335 2f1 o1 am,a=99.260(6)。,卢=101.223(8)。,y=94.805(8)。,v=3.425(3)am ,Oc=1.385 g・em。。,Z=6, (M0 Ka)=0.992 mm一,F(000)=I 474,最终偏 离因子R1=0.056 1,wR2=O.1128。在标题化合物的不对称单元中有3个单核铜(Ⅱ)配合物,且3个中心铜㈣离子的配位数不完全 相同,如Cu(1)离子的配位数是4,而Cu(2)和Cu(3)离子的配位数都是5。本文还测定了标题化合物的电化学性能和荧光性能,结 果表明:在电化学过程中配合物的电子转移是准可逆的.电子转移数为2个:配合物在478 nm的光激发下可发射荧光 关键词:铜(Ⅱ)配合物;二苯乙醇酸;晶体结构;电化学和荧光性能 中图分类号:0614.121 文献标识码:A 文章编号:1001.4861(2011)09—1847.05 Synthesis,Crystal Structure,Electrochemical and Luminescent Properties of a Copper(H)Complex with Benzilic Acid as Ligand YANG Ying-Qun CHEN Man—Sheng CHEN Zhi—Min LI Wei (Department ofChemistry and Materials Science,HengyangNormal University,Hengyang,Hunan 421008,China) Abstract:A complex[Cu(2,2'-bipy)(BAA)][Cu(2,2'-bipy)(BAA)(H20)]2・(H20)3(BAA=benzilic acid anion,2,2 - bipy=2,2'-bipyridine)has been synthesized.Crystal data for this complex are as follows:trielinic,space group P1,0= 1.121 7(5)nm,b=1.360 2(6)nm,c=2.335 2(10)nm,a=99.260(6)。,fl=lO1.223(8)。,y=94.805(8)。,v=3.425(3)nm , D。=1.385 g・cm。,Z=6,/z(Mo Ka)=0.992 mm~,F(O00)=I 474,final discrepancy factors R1=O.056 l,wR2=0.112 8. There are three mononuclear copper(1I)complexes in one asymmetric unit of the compound.where the three central Cu(II)ions are not all of the same coordination number.Cu(1)ion is tetra.coordinated,while Cu(21 ion and Cu(31 ion are both penta.coordinated.me cyclic vohammetric behavior and fluorescent property of the title compound were investigated.The results show that the electron transfer in the electrode reaction of the tilte complex is irreversible.and two electrons are involved in the oxidation of the title complex.When the exciting radiation setting at 478 nm.the title complex can give off lfuorescent emission.CCDC:788067. Key wor ̄:copper(H)complex;benzilic acid;crystal structure;electrochemical and lfuorescent property Studies of copper complexes have attracted much attention in the molecular construction and crystal active substances,metal—ion drugs,and models for protein—metal binding sitest .So far.some three。 engineering not only because they are useful models to design and study the magnetic—exchange interactions but also because most of them are also biologically 收稿日期:2010—11-08。收修改稿13期:2011-05—13。 nuclearf6- ̄.four-nuclear 】and six—nuclear[ 4]copper complexes with novel structures have been obtained by means of carboxylate ligands.It s woah noting that 衡阳市科技计划项(No.2009KJ26),湖南省重点建设学科资助项目。 通讯联系人。E-mail:yyingqun@126.corn 1848 无机化学学报 第27卷 studies in this field have been f0eused mainly on low sterie hindrance earboxylate hgands.Benzilic acid is a he restultant blue solution was filtrated.Then th,e filtrate was put at room temperature for slow carboxylic acid with high steric hindrance,and its complexes have not been reported much jn the 1itera— ture[ ~ts].volatiliz:ation.Blue roob.shaped single crystals suitable for X.-ray diffraction analysis were obtained af1[er three Therefore.it is meaningful to report our latest weeks.Yild:47%.IR(eKBr,cm ):3 400(w),1 647(vs), 1 597(m),1 445(s),1 310(s),779(s),710(s),560(m),576 (m),418(m). 1.3 Crystal structure determination study result:the novel eopper ̄}compound[Cu(2,2 一 bipy)(BAA)I[Cu(2.,2'-bipy)(BAA)(H20)]2-(H20)3. 1 Experimental 1.1 Mate—Lals and instrumenta ̄tin oCuprous chloride,2,2 bipyridine,triethylamine, acetic acid and sodium acetate trihydrate were of analytical grade and used without further puriifcation., while benzihc acid was prepared by ourselves.Crystal structure determination was carried out with a Rigaku SNTURN CCD elif.fraetometer.Luminescence spectra A crystal wih tdimensions of 0.20 mmx0.18 mmx 0.12 mm was chosen to be measured on a Bruker SMART APEX CCD diffraetometer equipped with a graphite-monochromatic Mo Ka radiation(A=0.07 1 073 nm)by using eo-q ̄scan mode at 1 13(2)K.Collected within the range of 1.53。≤0≤26.00。were a totall of 28 142 reflections,of which 13 387 were independent with Rim:0.038.9 356 were considered to be observed were recorded at room temperature with a W GY.10 qlfuorescence speetrophotometer.Cyclic vohammetry was conducted with an EC550 eleetroehemicaI analysis system. _>2 ∽)and used in the succeeding refinement.The crystal structure was solved directly with SHELXS一97 program【 .Corrections for Lp factors and empirical adsorption adjustment were applied and all non— hydrogen atoms were refined with anisotropic therma1 parameters.The final refinement including hydrogen 1.2 Synthesis of the complex A mixture of cuprous chloride f 1.29 mmo1)。 benzilic acid(0.67 mmoI)and 2,2 一bipyridine(0.19 mmol1 was dissolved in 1 2 mL ethano1.The pH value of atoms converged to Rl=O.056 1,wR2=O.1 12 8;w=l/[S (哟+(0.05 +1.55;PI,where P:(  ̄2E2)/3,(△/ ) = 0.000,S=I.054.Crystallographic data of the complex are showninTabh 1. the resuhant mixture was adjusted to about 5.0 by adding five drops of triethylamine solution.After the reaction was kept under water-bath at 343 K for 20 h。 CCDC:788067. Table 1 Crystallographic data of the rifle compound Empiircal formula Formula weighl C72H64Cu3N l4 1 427.91 Y/(。) V/rim 94.805(81) 3.425(31) Color Size/mm Blue 0.20x0..18x0.12 D/(g-cm 3) Z 1.385 2 0 range for data collection/(。) Crystal system Space group 1.53 to 26.00 Triclinic PI O0o1 【(MoKa)/mnl R[eflecfions collected 1474 0.992 2 8 142 a/nm 1.121 7(5) Independent reflections假.m) 1 3387(0.038 7) b/nm c/nm ot/(。) 1.3602(6'I 2.335 2(1 o1 99.260(6) Final【GooF R1, R2【,>2 (|『)】Rl,wR2(all data) 1.054 0A056 1,0.112 8 O.089 2,O.121 1 卢/(。) 101.223(8) Largest difference peak and hole/(e・nm一3) 543,一444 2 ReslllitS and discussion 2.1 Crystal structure analysis The crystal structure of the compound is revealed in Fig.1.Selected bond lengths and bond angles are shown in Table 2 and hydrogen bonds are shown in Table 3.As shown in Fig.1,the ittle compound consists 1850 无机化学学报 第27卷 and 0(8)locate at the equator plane;0(7)and N(6) occupy the axial positions.The sum of bond angles O(1W)一Cu(3)一N(5)(97.01(12)。), O(8)一Cu(3)一N(5) (158.43(1 3)。)and 0(8)-Cu(3)一O(1W)(104.08(1 1)。)is 359.52。.The Cu-O bond lengths differ to some extent. The Cu-O bonds formed by the earboxyl oxygen atoms of benzilic acid radicals cover Cu(1)-0(2)0.190 8(2)nm and Cu(2)一0(5)0.192 0(3)nm,cu(3)一o(8)0.195 7(3) nm,and their average length is 0.192 8 nm.On the other hand,the Cu—O bonds formed by the hydroxyl oxygen atoms from the benzilic acid anions include Cu(1)一O(1)0.187 9(3)nm and Cu(2)一O(4)0.192 2(2) nm,Cu(3)一0(7)O.191 0(2)nm and their average length is 0.190 4 nm.It is clear that the average length of the former type of Cu—O bonds is longer than that of the latter type,suggesting the coordination ability of the hydroxyl oxygen atoms is stronger than that of the carboxyl oxygen atoms from benzilic acid anions. Compared to hydroxyl oxygen atoms and carboxyl oxygen atoms,the coordination ability of water molecules is the weakest.The bond length of Cu(2)一 O(2W)and Cu(3)一O(1W)are 0.235 5(3)and 0.2.22 2(3) nm,respectively. In addition,there are strong hydrogen bonding interactions in the compound.Hydrogen bonding interactions could be observed in adjacent free water molecules.The free water molecules and the coordinated water molecules are linked by hydrogen bonds.The water molecules connect with benzilic acid radicals via hydrogen bonds. 2.2 Electrochemical property Fig.2 shows the CV curve of the compound.In the CV measurement,we employed a conventional three- electrode system where glass/C was chosen as the working electrode,a saturated calomel electrode(SCE) as the reference electrode,and a platinum electrode as the counter electrode.The compound was dissolved into the solvent of methanol,the resulted solution being of the concentration of 1 xl0 mol・L-1.HAc—NaAc solution fpH 4.81 was used as buffer solution.The scanning range was一0.5—1.0 V and the scanning rate was 1 50 mV・s~.The results show that there exists only one oxidation peak.The peak potential is 0.058 V, demonstrating that the electron transfer in the electrode reaction is irreversible. v/v Fig.2 Cyclic vohammogram of the title complex Under the same condition,the influence of potentila sscanning rate on the oxidation peak potential was studied in the range of 30—270 mV・s~.The result shows that the oxidation peak potentila shitfs to a more positive value with the increase of the scanning rate,and it is proportional to lgv in the range of 30-270 mV。s~.The linear regression equation is E (V)= 0.057 31gv——0.067 7 with the correlation coefifcient of 0.98 1 3.On the basis of the slope of Epa with lgv,the number of electrons involved in the oxidation of the compound can be evaluated.The o/n is calculated to be 1.03.Generally.the electron transfer coefifcient o/is about 0.5 in the totally ireversible electrode process. So,the value of n is about 2,indicating that two electrons are involved in the oxidation. 2.3 Fluorescent property The fluorescent properties of the compound and the free ligands were measured in the solid state at room temperature in the range of 460-540 am.Their emission spectra are shown in Fig.3.The compound exhibits one intense emission band at around 482 nm with the exciting radiation at 478 nm(curve b).Under the same condition,the free ligands benzilic acid and 2,2 -bipyridine display their emission band at about 500 nm(curve a)and 497 nm(curve c),respectively. The emission band of the compound is similar to the ligands,indicating that intraligand excitation is responsible for the emission of the compound.Clearly, blue—shitf of emission occurs in the compound probably 第9期 杨颖群等:二苯乙醇酸铜配合物的合成、晶体结构、电化学和荧光性质 1851 because of the coordination of ligandst2 ̄ ̄. Wavelength/am Fig.3 Emission spectra of the title complex and ligands i 13 solid state at room temperature References: [1]HE Shui—Yang(何水样),CAO Wen—Kai(曹文凯),CHEN Jun一 ¨(利),et a1.Chem.tJ=Chinese Univ.(Gaodeng Xuexiao Huaxue Xuebao),2002,23(6):99 1—995 【2】DeyM,RaoCP,SaarenketoPK,et a1.Inorg.Chem.Commun., 2002,5:380-382 [3]ZHAO Yan( ̄焱),LI Li(李莉),LIU Yu( ̄J育).Chem.上 Chinese Univ.(Gaodeng Xuexiao Huaxue Xnebao),2002,23 (12):2272・2277 f41 SUN You.Min(孙友敏),WANG Ruo-xi(王若曦),LIU Cheng— Bu(刘成卜).Chem.上Chinese Univ.(Gaodeng Xuexiao Huaxue Xuebao),2005,26(2):294—298 【5】JIA Li.Hui( ̄丽慧),LIU Zu—Li(刘祖黎),LIU Wei( ̄J蔚), et a1.Chinese‘J=Inorg.Chem.(Wuji Huaxue Xuebao),2008,24 (2):285-289 [6]Escovar R M,Thumton J H,Ould・Ely T,et a1.Z Anorg.Af Chem.,2005,631:2867・2869 [7】ZHANG Rui.Bo(张瑞波),ZHANG Jian( ̄健),WEN Yi—Hang (温一航),et a1.Chiense tJ=Struct.Chem.(Jiegou Huaxue), 2005,24(1 1):1302—1305 【8】Chen X B,Chen B,Li Y Z,et a1.App1.Organomet.Chem., 2007.21:777-779 [91 LI Wei(李薇),LI Chang-Hong(李昶红),YANG Ying-Qnn(杨 颖群),et a1.Chiense Struct.Chem.(Jiegou Huaxue),2006, 25(11):1331-1336 【10]Chandrasekhar V,Sasikumar P,Boomishankar R,et a1.Inorg. hCem.,21)06,45:3344—3349 [1 1]Antsyshkina A S,Sadikov G G,Poznyak A L,et a1.Russ..J= Inorg.Chem.,2006,51:283—286 【12]Mezei G,Rivera-Carrillo M,Raptis R G.1norg.Chim.A cta ̄ 2O04.357:3721—3724 [13]Ruiz-Perez C,Sanehiz J,Hernandez M M,et a1.Inorg.Chem., 2000,39:1363-1368 [14]Filippova I G,Kravtsov V K,Gdanets V M.Russ Coord. Chem.,2000,26:860-863 [15]Carballo R,Castineiras A,Covelo B,et a1.Polyhedron,2004, 23:1505—1509 [16]Carballo R,Covelo B,Garcia—Martinez E,et a1.App1. Organomet.Chem.,2005,19:394—398 【17]YANG Ying—Qun(杨颖群),LI Chan Hong(李昶红),KUANG Dai-Zhi(邝代治),et a1.Chinese Inorg.Chem.(Wuji Huaxue Xuebao),2006,22(2):303—306 [18]YANG Ying—Qun(杨颖群),LI Chang-Hong(李昶红),LI Wei (李薇),et a1.Chiense lnorg.Chem.(Wuji Huaxue Xuebao), 2009,25(4):730—733 [19]Sheldrick G M.SHELX一97,Programfor teh Solution and teh R ̄ifnement of Crystal Structures,University of Gottingen, Germany,1997. 【20]LI Wei—Qi(李伟琦),FENG xi(封霞),FENG Yun—Long(7-q云 龙),et a1.Chiense.J=Inorg.Chem.( Huaxue Xuebao), 2008,24(6):873 879