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1、第32卷第4期2016年4月无 机 化 学 学 报CHINESE JOURNAL OF INORGANIC CHEMISTRYV0132 No4738744两个基于22 7联吡啶55 7二羧酸配体构筑的碱土金属配合物的合成、晶体结构及其光致发光性质区泳聪 钟均星 宋萦怡 朱岚岚 吴建中(广州市能源转化与储能材料重点实验室，华南师范大学化学与环境学院，广州 510006)摘要：从2，2 7一联吡啶一5，5一二羧酸配体出发，利用溶剂热的方法，合成了两种新颖的碱土金属配位聚合物【Ca(bpdc)(DMF)：(H20h。(1)和Mg(bpdc)(H：0)，。(2)，并且对其进行r元素分析、红外光谱、热
2、重分析和光致发光性质表征。单晶结构分析表明，配合物1和2都是一维链结构并且通过分子间的氢键和7r一丌堆积作用连接成三维的超分子结构。有趣的是，固态荧光光谱显示两种结构的荧光出现了明显的不同，联系结构分析推断可能是有机配体的不同配位构象导致的。关键词：碱土金属配合物；溶剂热合成；构象；光致发光中图分类号：061423+1；061422 文献标识码：A 文章编号：10014861(2016)04073807DoI：10118621CJIC2016092Two 1D Chain Structures Derived from AlkalineEarth Metal Complexesand 2,2-
3、Bipyridine-5，5-dicarboxylate Ligand：Syntheses，Crystal Structures and Luminescent Properties0U Yong-Cong。ZHONG JunXing SONG YingYi ZHU LanLan WU Jian-Zhong(Guangzhou Key Laboratory ofMaterials for Eriergy Conversion and Storage，School of Chemistry and Environment，South China Normal University,Guangzh
4、ou 5 10006，China)Abstract：Two alkaline-earth metal coordination complexes，Ca(bpdc)(DMF)2(H20)d。(1)andMg(bpdc)(H20)3。(2)(H2bpdc=2，2一Bipyridine一5，5 7dicarboxylic acid)，have been obtained via solvothermal conditions and characterizedby elemental analysis，IR spectra，thermogravimetric analysis and photol
5、uminescent measurementSingle crystalXrav diffractions reveal that complexes 1 and 2 are 1 D chain structures which are further connected into 3Dsupramolecular structures by hydrogen bonding interactions and 77订stacking interactionsItS noted that thesolidstate fluorescent emissions of 1 and 2 are dif
6、ferent in related to the different conformation modes of thebpdcligandCCDC：1444695，1；1444696，2Keywords：alkaline-earth metal complexes；solvothermal syntheses；conformation；photoluminescenceMetal coordination polymers(MCPs)have beenwidely researched in recent years not only due to theirnovel and intrig
7、uing topological structures，but alsobecause of various potential applications in manyaspects，for example，as porous，magnetic，luminescentand catalytic materials【141Among themtransition metaland lanthanide metal complexes have been extensivelystudied，but there are relatively less reported for thealkali
8、ne-earth metal complexes【5As the characteristicsof alkalineearth are intriguing for their electronic收稿日期：2015-1230。收修改稿日期：201603Ol。国家自然科学基金(No21401058)和广东普通高校青年创新人才项目(No2014KQNCX058)资 。+通信联系人。E-mail：ouyongcongmscnueducn；会员登记号：S06N6724M1506。万方数据第4期区泳聪等：两个基于2，2 7一联吡啶一5，5 7一二羧酸配体构筑的碱土金属配合物的合成、晶体结构及其光致发
9、光性质 739structures，wide emission peaks and large Stokes shift，the syntheses of alkaline-earth complexes would bepregnant2,2 7一Bipyridine-5，5一dicarboxylic acid fH2bpdc)，as a muhifunctional bridging ligand，has been used toconstruct various MCPs9According to our previousstudiesll6。mthe different coordin
10、ation modes might lcadto the different propertiesIts interesting that H2bpdccan be fixed in the structure in two modes：the Natoms are in transor cis-positionTo our best knowledge，the researches on the different photoluminescentproperties based on the different conformation ofH2bpdc are rareI呲1 81Her
11、ein，two novel coordinationcomplexes，Ca(bpdc)(DMF)2(H20)2。(1)andMg(bpdc)(H20)32)，are constructed via solvothermal conditionsand characterized by elemental analysis，IR spectra，thermogravimetric analysis and photoluminescentmeasurementTo be noticed that the solidstate fluorescent emissions of 1 and 2 a
12、re difierent in relatedto the different conformation modes of the bpdc2一ligand1 Experiment11 Materials and physical measurementsThe chemicals and solvents were commerciallyavailable and used without further purificationC，H，and N microanalyses were carried out with ElementarVarioEL CHN elemental anal
13、yzerFTIR spectrawere recorded on Nicolet FT-IR-1 70SX speetrophoto-meter in KBr tablets in the range of 4 000400 cmX-ray powder diffraction(XPRD)intensities for poly-crystalline samples of complex 1 and 2 were measuredat 293 K on Bruker D8 Advance Diffratometer(CuKsA=01 54 056 nml by scanning over t
14、he range ofo-50。(o-50。for 2)with step of 02虬sSimulatedXPRD patterns were generated with MercuryThermogravimetric analyses were performed onPerkinElmer TGA 7Luminescent spectra for solidstate samples were recorded on Hitachi F一2500 atroom temperature with a xenon arc lamp as the lightSOUrce12 Synthes
15、is of【Ca(bpdc)(DMF)2(H20)21。(1)A mixture of H2bpdc(01 mmol，24 rag)，CaCl2(01 mmol，1 20 mg)and succinic acid(01 mmol，1 20mg)in DMF(4 mL)was sonicated 5 min and thenheated in a stainless steel reactor with Teflon liner(23mE)at 1 20 c|C for 72 h and cooled to ambient temperatureat a rate of co5 qCh一to g
16、ive colorless sheet crystals(Yield based on H2bpdc：35 mg，7 16)Elementalanalysis calcdfor C18H240sN4Ca()：C 4654，H 521，N 1206；Found()：C 4635，II，529，N 1 19613 Synthesis of【Mg(bpdc)(H20)3。(2)A mixture of H2bpdc(01 mmol，23 rag)，MgCl2(01 mmol，90 mg)and two drops triethylamine inDMF(3 mL)and H20(2 mL)was s
17、onicated 5 min andthen heated in a stainless steel reactor with Teflonliner f23 mE)at 120for 72 h and cooled to ambienttemperature at a rate of co5 cch。1 to give colorlesscolumn crystals(Yield based on H2bpdc：27 mg，894)Elemental analysis calcdfor C12H1207N2Mg()：C4496，H 377，N 874；Found()：C 4510，H，379
18、，N 88114 Xray crystallographyDiffraction data for compound 1 was collected onRigaku RAXIS SPIDER Image Plate diffractometerwith graphitemonochromated Mo Ka radiation fA=007 1 073 nm)at 150(2)KDiffraction data for compound 2 was recorded on Bruker smart ApexCCDarea detector diffractometer fMo Ks radi
19、ation。A=007 1 073 nml at 296(21 KThe intensities were integrated using SAINT+Corrections for Lorentz andpolarization effects were appliedAbsorption correctionswere applied by using the multiscan programSADABS【19】The structures were solved by directmethod，and all non-hydrogen atoms were refinedanisot
20、ropically by leastsquares method on F 2 usingthe SHELXTL programThe organic hydrogen atomswere generated geometrically；the aqua hydrogenatoms were located from difference maps and refinedwith isotropic temperature factorsCrystal data as wellas details of data collection and refinements for a11compou
21、nds are summarized in Table 1Table 2 andTable 3 give the data of selected bond lengths andangles and the hydrogen bond parameters for complexes1 and 2 respectivelyCCDC：1444695，1：14446962万方数据740 无机化学学报 第32卷Table 1 Crystal data and structure refmements for 1 and 2Complex 1 2Empirical formula GHl204N2C
22、 a【15 C12H1207N2MgFormula weight 23225 32055Crystal system Tficlinic MonoclinicSpace group P1 P2lcnnm 0638 65(61 1483 4(71bnm 0784 10(71 1197 6(51cnm 1170 04(101 0752 7(41“(o)80397(2) 90卢(。)80123(3) 96766(917(o) 66710(2) 90Vnm3 0527 01(8) 1328 O(101Z 2 4D。(gcm-3) 1464 1603pmm一1 O351 0174Reflections
23、collected 4 947 7 375Unique reflections 2 256 2 813S 1076 1025R，8，wRzb(，2口(J)0055 1，0 138 5 0 073 70209 9R-j棚2b(all data) 0073 6，0152 2 O124 6，0237 7“RFHFoMF3 MYIFol，6 wR：=(野一哟2Y,4rg)q“Table 2 Selected bond lengths(nm)and angles(。)for 1 and 21Ca(1)一0f1)0228 5(4) Ca(1)一O(3)0235 4(3) Ca(I)一o(1w)0234 9
24、f2)Ca(1)。O(1a)0228 5(4) Ca(1)一0(3a)0235 4(3) Ca(I)一O(1Wa)0234 9(2)O(1)。Ca(1)一O(1a) 180 O(1a)-Ca(1)一0(18692(5) O(1W)Ca(1)0(3)8984(5)O(1)。Ca(1)一O(1W) 9307(6) o(1a)一Ca(1)一O(1Wa) 9307(4) O(1W)Ca(1)0(3a) 9015(8)O(1)。CaO)一O(1Wa)8692(4) O(1a)-Ca(1)-0(3)8864(6) O(1Wa)Ca(1)一0(3) 9015f6)O(1)。Ca(1)一0(3) 9135(7
25、) o(1 a)-Ca(1)一O(3a) 9135(8) O(1Wa)一Ca(1)一O(3a)8984(7)O(1)。Ca(1)一O(3a)8864(4) O(1W)-Ca(1)-O(1Wa) 180 0(3)Ca(1)0(3a) 1802Mg(1)一O(1a) 0201 8(3) Mg(1)-0(3即 0205 3(4) MS(I)N(1) 0 222 1(4)Mg(1)一0(2聊 0203 3(4) Mg(1)-0(1聊0208 2(4) Mg(1)一N(2)0225 3(4)O(1a)。Mg(1)。O(2W) 90 30(15)0(3聊-Mg(1)-O(1W)8560(15) O(1a)
26、Mg(1)N(2) 16835(15)O(1a)一Mg(1)一0(3聊 10496(15) O(1a)Mg(1)一N(1) 9487(15) 0(2聊一Mg(1)N(2) 921 1(15)O(2W)。Mg(1)。0(3聊 91 26(16) O(2W)-Mg(1)-N(1) 93 97(16) o(3w)一Mg(1)N(2)8638(14)O(1a)。Mg(1)-0(1 W) 9321(15)0(3聊一Mg(1)一N(1) 15946(15) O(1W)Mg(1)一N(2)8491(14)O(2W)。Mg(1)一O(1W) 17579(15) O(1W)一Mg(1)一N(1)8805(15)
27、 N(1)Mg(1)N(2) 7359(14)Symmetry codes：a：一x+l，y+1，-z+2 for 1；a：一z，y+l2，-z+l2 fjr 2Table 3 Hydrogen bond parameters for 1 and 2DHA d(DH)nm d(HA)，nm d(DA)nm _(DHA)(。)lO(1W)H(1WA)0(2a) 0091 O176 0266 0(31 1708万方数据第4期区泳聪等：两个基于2，2联吡啶5，5 7二羧酸配体构筑的碱土金属配合物的合成、晶体结构及其光致发光性质 74lContinued Table 30(1聊一H(1WA)0(3c)
28、 0085 0195 O275 0(5) 15590(1w)一H(1WB)O(2d) O085 0197 0272 1(5) 1474O(2W)一H(2WA)O(4e1 0085 0194 0276 9(5) 1646O(2W)一H(2WB)0(20 0085 O192 0275 7(51 1677O(3W)一H(3WA)O(3e)0085 0191 0271 9(5) 15970(3聊-H(3WB)O(39) O085 0192 0271 6(5) 1544Symmetry codes：a：x+l，y，。；b：一x+l，y+1，-z+1 for l；c：一x+l，y+l2，-z+12 for
29、 22 Reslllis and discussion21 Crystal structuresSingle crystal structure shows that complex 1crysyallizes in P1 space group and contains halfcalcium ion，half bpdcligand，one DMF moleculeand one water molecule in asymmetric unit(Fig1a)Ca2+ion is surrounded with six oxygen atoms from twocarboxylate gro
30、ups of bpdc2。ligands，two water mole-clues and two acyl groups of DMF moleculesThebpdc2一ligands connect two Ca atoms as bridges to form(a)一Y，-z；d：一并，y，喀；e：一并+】，一Y，z+1；t：-X，-y，-z+l；g：菇+1，an infinite chain，and the nitrogen atoms of ligandwere fixed in the lattice in transposition(Fig1 b)Since only one
31、oxygen atom of the carboxylate groupcoordinated with Ca2+ion，the free oxygen atom cangenerate two hydrogen bonds with two hydrogen atomsin two water molecules(Table 3)to expand into twodimensional layer(Fig1 e)Then 2D layers are conne-cted into 3D supramolecular structure via the bpdc2一ligands(Fig1d
32、)Complex 2 is also a 1 D coordination chainstructure composed of one magnesium ion，one bpdc2一(b)H atoms with carbon atoms are omitted for clear in(d)；Symmetry codes：a：x+l，Y，z；b：叫+1，_y+】，-z+lFig1(a)Coordination environment of Ca“and bpdc2。ligand with ellipsoids at the 50probability level for 1；(b)Vie
33、w of I D coordination chain；(C)2D layer connected by hydrogen bonds；(d)3D supramolecularstructure of 1万方数据742 无机化学学报 第32卷H atoms with carbon atoms are omitted for clear；Symmetry codes：a：一x，y+l2，-z+l2；b：一x，广12，一z+l2；c：一x+l，-y，-z；d：，-y，-z；e：一x+l，-y，-z+l；g：一x+l，妒1，2，-z+l2Fig2(a)Coordination environment
34、s of Mg“ion and bpdc2ligand with ellipsoids at the 50probability level for 2；(b)Perspective view along caxis of the I D watercarboxylic group hydrogen bonding chain；(C)1 D coordinationchains stacking via丌一7r interactions；(d)Three dimensional supramolecular structure of 2ligand and three coordination
35、asymmetric unit(Fig2a)M92+water molecules in theion is coordinated withtwo nitrogen atoms and one oxygen atom from a bpdc2一ligand and three water moleculesItS different fromcomplex 1 that the coordination mode of bpdc2一ligandin 2 iS Tshape connection with metal atoms throughoxygen atom in one carbox
36、ylate group and two nitrogenatoms which were fixed in cispositionTherefore1 Dz-type chains are constructed and stacking along Caxis via 7r7r interactions(d=0328 nm)(Fig2b)To benoticed that the coordinated water molecules 03w arehydrogen bonded with 03 atoms and then forms aninteresting infinite hydr
37、ogen bonding chain whichfurther connects with the other molecules，O l w and02w，with hydrogen bonds along c-axis as branches(Fig2c，Table 3)Due to the hydrogen bondinginteractions above，1D chains could be linked into 3Dsupramolecular structure(Fig2d)22 Thermogravimetric analysisThermogravimetric(TG)an
38、alysis was carried outto examine the thermal stabilities and confirm thestructures of complexes 1 and 2 together with elementalanalysisThe purity of all the powder samples areconfirmed by PXRD(Supporting information)All thecomplexes are heated in nitrogen from room temperatureto 700 cCFor 1 fFig3a)a
39、 weight loss oecuring at thebeginning is related to the poor crystal stabilityTheweight lOSS before 1 50of 381 0corresponds tothe weight of the coordinated DMF and water moleculesAnd then there is a long plateau emerging until thetemperature reaehs 450at which the organicligands begin to decomposeFi
40、g3b shows that complex2 can be stable up to the temperature of 1 10andthen a quick weight loss of 1617from 1 10 to 150corresponds to the loss of three coordinated watermolecules(1685)There is a long plateau before 420at which the bpdcligands begin to decompose23 Infrared spectraAs is shown in Fig4，i
41、n the high-frequency region，the spectra of 1 and 2 are dominated by an intenseand wide absorption centered at 3 430 and 3 400 cm，which arise from aoH1 stretching modes of latticewater moleculest2”Moreoverthere are similar absorption peaks in two spectra，1 670，1 250 em一1 for 1 and万方数据区泳聪等：两个基于2，2一联吡啶
42、一55 7一二羧酸配体构筑的碱土金属第4期 配合物的合成、晶体结构及其光致发光性质 743装呈挲Temperature器羔呈9TemperatureFig3 Thermogravimetric analysis CHIVES of 1 a)and 2(b)1 685，1 298 CHIfor 2，which are cortesponding tothe。and。absorption ofC00一groupsl221and the Avof 420 cm一1 for 1 and 387 cm一1 for 2 indicate theunidentate coordination mode of
43、 the carboxylategroups in 1 and 2The absorption bands of pyridylrings are assigned to the peaks of 1 590 and 1 410 cmFor 1，there are extra peaks of DMF molecules at2 922 cm一1 and 2 854 cmiwavenumbercmFig4 IR spectra of 1 and 224 Luminescent propertiesThe phocoluminescent properties have also beenmea
44、sured in solid state at room temperature(Fig5)The emission peaks of 1(432 and 500 nm)and 2(442rim)，which could be attributed to the 7r7r术transition within the pyridyl rings of the ligand，arehypochromatic shift compared with that of the ligand(455 and 547 rim)ItS interesting that there is onlyone emi
45、ssion peak for 2 whereas H2bpdc ligand and 1exhibit two emission peaksSince the PXRD data ofraw materials iS in accordance with the simulatedPXRD data of the reported crystal structure【18】weconfirmed that the conformation of H2bpdc ligand istransmode structureSo，the disappearance of theemission peak
46、 for 2 might be associated with the csconformation of the ligand in the crystal structure of 2，which iS in accordance with the literaturd241彳日占罱旦三WavelengthBIIlFig5 Solidstate luminescent spectra of H2bpdc，1 and 23 ConclusionsIn summary。two alkalineearth metal complexeshave been obtained via solvoth
47、ermal conditionsBothof them are 1 D coordination chain structures wberecomplex 2 contain interesting hydrogen bondingchainsLuminescent properties show that emissionpeaks of 2 are different from that of 1，which aresimilar to the emission peaks of organic ligandSupporting information is available at h
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