title: First quadruple-glycine bridging mono-lanthanide-substituted borotungstate hybrids.
abstract: A class of novel organic-inorganic hybrid lanthanide (Ln)-substituted Keggin-type borotungstates K4Na4H4[Ln2(gly)4(α-BW11O39)2]·23H2O [Ln = Ce3+(1), Pr3+(2), Nd3+(3), Sm3+(4), Eu3+(5), Tm3+(6); gly = glycine] have been synthesized from the reaction of K8[BW11O39H]·13H2O, NaAc·6H2O and Ln(NO3)3·6H2O by employing gly ligands as structure-stabilizing agents in the conventional aqueous solution system and structurally characterized by elemental analyses, IR spectroscopy, thermogravimetric (TG) analyses, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The common prominent structural feature of isomorphic 1-6 is that all of them consist of two mono-Ln-substituted Keggin [Ln(α-BW11O39)]6-fragments linked by four gly ligands, furnishing an intriguing dimeric assembly of the quadruple-gly-connective mono-Ln-substituted borotungstate, in which each carboxylic oxygen atom from gly ligands is bound to Ln3+cations in the μ2-O or μ3-O mode. To the best of our knowledge, 1-6 represent the first examples of inorganic-organic hybrid Ln-substituted borotungstates functionalized by quadruple amino acid bridges. The solid-state photoluminescence properties of 3-5 have been determined at ambient temperature and the photoluminescence emission spectra exhibit the characteristic emission bands derived from Ln3+centers. The thermostability of 1-6 has been studied and the thermal decomposition procedure of 3 has been comprehensively investigated with the assistance of variable-temperature PXRD patterns and variable-temperature IR spectra. Furthermore, magnetic susceptibility measurements of 1, 2 and 4 have been conducted.
authors.affiliation: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China. ljchen@henu.edu.cn zhaojunwei@henu.edu.cn.
authors.forename: Jiancai
authors.initials: J
authors.lastname: Liu
authors.affiliation: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China. ljchen@henu.edu.cn zhaojunwei@henu.edu.cn.
authors.forename: Jing
authors.initials: J
authors.lastname: Yu
authors.affiliation: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China. ljchen@henu.edu.cn zhaojunwei@henu.edu.cn.
authors.forename: Qing
authors.initials: Q
authors.lastname: Han
authors.affiliation: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China. ljchen@henu.edu.cn zhaojunwei@henu.edu.cn.
authors.forename: Yue
authors.initials: Y
authors.lastname: Wen
authors.affiliation: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China. ljchen@henu.edu.cn zhaojunwei@henu.edu.cn.
authors.forename: Lijuan
authors.initials: L
authors.lastname: Chen
authors.affiliation: Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, P. R. China. ljchen@henu.edu.cn zhaojunwei@henu.edu.cn and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
authors.forename: Junwei
authors.initials: J
authors.lastname: Zhao
mesh_terms: D001895:Boron / Q000737:chemistry*; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D005998:Glycine / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013818:Thermogravimetry; D014414:Tungsten / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D001952:Bridged-Ring Compounds; D028581:Lanthanoid Series Elements; D008024:Ligands; D009942:Organometallic Compounds; D001895:Boron; D005998:Glycine; D014414:Tungsten