2-氯-4-氟苯甲酸与5%2C5%27-二甲基-2%2C2%27-联吡啶镧系配合物的晶体结构、光谱和热行为.pdf

第39卷第9期2023年9月Vol.39 No.918071816无机化学学报CHINESE JOURNAL OF INORGANIC CHEMISTRY收稿日期：20230227。收修改稿日期：20230624。国家自然科学基金(No.22273015)资助。通信联系人。Email：，，2氯4氟苯甲酸与5，5二甲基2，2联吡啶镧系配合物的晶体结构、光谱和热行为杜丹丹1郝娅帆1王鑫鑫1赵金金,1任宁,2张建军,1(1河北师范大学分析测试中心，化学与材料科学学院，石家庄050024)(2邯郸学院化学化工与材料学院，河北省杂环化合物重点实验室，邯郸056005)摘要：合成并表征了2个双核配合物Pr(2Cl4FBA)3(5，5DM2，2bipy)2(1)和Dy(2Cl4FBA)3(5，5DM2，2bipy)22(2Cl4FHBA)(2)，其中2Cl4FHBA=2氯4氟苯甲酸，5，5DM2，2bipy=5，5二甲基2，2联吡啶。配合物1以八配位的Pr3+为中心，其周围的配位环境为扭曲的三角十二面体。配合物2的结构是独特的，它包含2个自由的2氯4氟苯甲酸分子，并以九配位的Dy3+为中心与周围的氮、氧原子形成扭曲的三棱镜几何构型。这2个配合物均结晶于三斜晶系P1空间群，并通过氢键相互作用和堆积作用形成了一维和二维超分子结构。研究了配合物的热分解过程，结果表明配合物1和2分别分为4步和5步进行分解。同时对配合物的三维红外堆积图进行了研究，结果表明，整个热分解过程中释放出的主要气态产物是水、二氧化碳和有机小分子碎片。配合物2的荧光性质研究表明，它可以发射出Dy3+的特征跃迁对应的荧光。关键词：晶体结构；镧系配合物；热化学性质；光谱中图分类号：O614.33+4；O614.342文献标识码：A文章编号：10014861(2023)09180710DOI：10.11862/CJIC.2023.138Crystal structure,spectra,and thermal behavior of lanthanide complexes with2chloro4fluorobenzoic acid and 5,5dimethyl2,2bipyridineDU DanDan1HAO YaFan1WANG XinXin1ZHAO JinJin,1REN Ning,2ZHANG JianJun,1(1Testing and Analysis Center,College of Chemistry&Material Science,Hebei Normal University,Shijiazhuang 050024,China)(2Hebei Key Laboratory of Heterocyclic Compounds,College of Chemical Engineering&Material,Handan University,Handan,Hebei 056005,China)Abstract:Two binuclear complexes Pr(2Cl4FBA)3(5,5DM2,2bipy)2(1)and Dy(2Cl4FBA)3(5,5DM2,2bipy)22(2Cl4FHBA)(2),where 2Cl4FHBA=2chloro4fluorobenzoic acid and 5,5DM2,2bipy=5,5dimethyl2,2bipyridine,have been fabricated and characterized.The two complexes crystallize in the P1 spacegroup of the triclinic crystal system,featuring 1D and 2D supramolecular structures.The structure of complex 2 isfascinating,containing two free 2Cl4FHBA molecules,which are rare in lanthanide complexes.A threedimensional infrared stacking diagram of the gas phase products indicates that the main gaseous products released overthe whole decomposition process are water,carbon dioxide,some gaseous molecules,and the gaseous organic fragments.Also,the fluorescence property of complex 2 has been studied.CCDC:2051811,1;2051810,2.Keywords:crystal structure;lanthanide complex;thermochemical property;spectroscopy无机化学学报第39卷Lanthanide elements not only have a unique 4felectronic layer structure and attractive structure butalso have potential applications in magnetism,catalysis13,sensing materials46,and luminescent materials79.Currently,lanthanide complexes of various structural motifs of 1D,2D,and 3D have been synthesized.Unfortunately,due to the spinblocking transitions ofthe ff transition,the excitation efficiency of lanthanideion(Ln3+)is reduced10.Moreover,the most commoncoordination numbers of lanthanide complexes areeight and nine,and the geometric coordination configurations are diverse.Therefore,the factors required tocontrol the synthesis of structurally desirable lanthanide complexes remain a great challenge1112.Fortunately,the common way to avoid the above defects is toselect organic ligands with strong absorption ability,and then the absorbed energy is transferred from theligand to lanthanide ions through a nonradiative process1315.In addition,it is commonly admitted that lanthanides have a strong affinity for oxygen atoms.Therefore,oxygencontaining organic ligands can be used forthe synthesis of lanthanide complexes1617.Carboxylicacid ligands are the most widely used ligands,acting as“antennas”18and having flexible coordination modesand strong coordination ability.The lanthanide complexes constructed by them have become the focus ofcurrent coordination chemistry research.In this work,two new lanthanide complexes Pr(2Cl4FBA)3(5,5DM2,2bipy)2(1)and Dy(2Cl4FBA)3(5,5DM2,2bipy)22(2Cl4FHBA)(2),where 2Cl4FHBA=2chloro4fluorobenzoic acidand 5,5DM2,2bipy=5,5dimethyl2,2bipyridine,have been prepared.The two complexes were fullycharacterized by singlecrystal Xray diffraction,powder Xray diffraction(PXRD),IR spectra,Raman spectra,and elemental analysis.Moreover,thermogravimetrydifferential scanning calorimetry(TGDSC)/FTIRtechnology was employed to study the thermal behaviorof the obtained complexes.In addition,the fluorescence property of complex 2 has been studied.1Experimental1.1Materials and general methodsThe contents of carbon,hydrogen,and nitrogenwere acquired on a Vario EL element analyzer,while the metal content was assayed using the EDTAtitration method.Raman spectra were recorded by scanning 64 times with the BRUKER VERTEX70 FTIRRAMAN instrument under an excitation power of300 mW and liquid nitrogen cooling.The PXRD datawere obtained from a Bruker D8 Advance Xray diffraction at a working voltage of 40 kV and a working current of 40 mA in a 2 range of 545 with Cu K radiation(=0.154 18 nm)at 298 K.TG DTG(derivative thermogravimetry)/DSC andevolved gas analysis of the obtained lanthanide complexes were carried out using a NETASCH STA 449 F3instrument with a Bruker TENSOR 27 Fourier transform infrared spectrometer.Also,the luminescencespectra were measured on FS5 spectrometer.1.2Synthesis0.06 mmol 2Cl4FHBA and 0.2