Crystal Structure and Fluorescent Study of a Terbium(Ⅲ) Coordination Polymer

A novel Tb（Ⅲ） coordination polymer [Tb（bpapO2）2（NO3）3]n [bpapO2 = N2,N6- bi（pyridin-2-yl）pyridine-2,6-diamine-N,N＇-dioxide-dioxide] has been synthesized and it exhibits terbium’s characteristic fluorescent emission under UV radiation of 326 nm at room temperature. X-ray structural determination indicates that each terbium（Ⅲ） ion, centered in TbO8 core, connects to three adjacent coordinate centers via a bi-dentate ligand bpapO2, forming a one-dimensional coordination polymer. The compound crystallizes in the triclinic system, space group P1, with a = 11.2271（5）, b = 11.7997（5）, c = 14.8016（6） Ⅲ, α = 72.7060（10）, β = 89.9630（10）, γ = 66.7680（10）o, Z = 2, Dc = 1.822 g/cm3, V = 1705.14（13） Ⅲ3, F（000） = 932, the final R = 0.0340 and wR = 0.0669 for 4812 observed reflections with I 2σ（I）.

Preparation, Structure, Photoluminescence and Energy Transfer Mechanism of a Novel Holmium Complex

A novel holmium complex [Ho(HIA)_2(H_2O)_4(NO_3)](NO_3)_2(1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system: a = 14.4797(7), b = 12.4768(2), c = 13.3471(5) ?, β = 118.690(4)°, V = 2115.26(13) ?~3, C_(12)H_(16)HoN_5O_(17), Mr = 667.23, Z = 4, Dc = 2.095 g/cm^3, μ(Mo Kα) = 3.838 mm^(–1) and F(000) = 1304. The crystal structure of 1 is characterized by an isolated structure. Solid-state photoluminescence experiment uncovers that it shows yellow light emission. The emission bands are originated from the characteristic emission of the 4 f electrons intrashell transition of the ~5S_2 → ~5I_8 and ~5F_5 → ~5I_8 of the Ho^(3+) ions. Energy transfer mechanism is explained by the energy level diagram of the Ho3+ ion and the isonicotinic acid ligand. It has remarkable CIE chromaticity coordinates of(0.4929, 0.4632), so it may be a promising color converter for lighting and displays.

Crystal Structure and Properties of [PrCl(H_2O)_3(L)(HL)]_nnCl(HL=3-Hydroxy-2-methylquinoline-4-carboxylic acid) with One-dimensional Chains

A novel praseodymium complex [PrCl(H_2O)_3(L)(HL)]_nnCl(1, HL = 3-hydroxy-2-methylquinoline-4-carboxylic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in P2_1 space group of the monoclinic system, with a = 7.3146(2), b = 9.3963(3), c = 17.4872(5) ?, β = 96.818(3)°, V = 1193.40(6) ?~3, C_(22)H_(23)Cl_2N_2O_9Pr, M_r = 671.23, Z = 2, D_c = 1.868 g/cm^3, μ(MoKα) = 2.322 mm^(-1) and F(000) = 668. The praseodymium ion is surrounded by seven oxygen atoms and one chlorine atom to yield a slightly distorted square antiprism. Complex 1 is characterized by a one-dimensional chain-like structure. A two-dimensional supramolecular layer is formed via hydrogen-bonding interactions. Solid-state photoluminescence spectrum reveals that it shows red emission. The emission bands are ascribed to the characteristic emission of the 4 f electron transitions of ~3P_0 → ~3H_J(J = 5 and 6) and ~3P_0 → ~3F_4 of Pr^(3+) ions. Solid-state UV/Vis diffuse reflectance spectroscopy exhibits that it has an optical band gap of 2.75 eV.

Upconversion Photoluminescence and Energy Transfer Mechanism of a Novel Terbium-mercury Compound

A novel terbium-mercury complex [Tb(IA)3(H3 O)2]2 n(2 n HgCl4)(n Hg2 Cl5)·n H3 O· 3 n H2 O(1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system with a = 24.2347(5), b = 20.8342(6), c = 15.3206(3) ?, β = 128.257(2)°, V = 6074.3(2) ?3, C36H41Cl13Hg4N6O20Tb2, Mr = 2458.80, Z = 4, Dc = 2.689 g/cm3, μ(Mo Kα) = 13.014 mm–1 and F(000) = 4520. The crystal structure of 1 is characterized by a one-dimensional(1-D) chain-like structure. Solid-state UV/Vis diffuse reflectance spectrum reveals the existence of a wide optical band gap of 3.36 eV. Solid-state photoluminescence experiment uncovers that it shows reddish brown upconversion emission. The emission bands are originated from the characteristic emission of the 4 f electrons intrashell transition of the 5D4 → 7 FJ(J = 6, 5, 4) of the Tb3+ ions. Energy transfer mechanism is explained by the energy level diagram of the Tb3+ ion and the isonicotinic acid ligand. It shows a remarkable CIE chromaticity coordinates(0.4158, 0.4005).

Hydrothermal Synthesis and Crystal Structure of a Novel Selenite-chloride:[Cd_4(SeO_3)_2Cl_4(H_2O)]_n with a Three-dimensional Framework

A novel three-dimensional（3-D） compound [Cd4（SeO3）2Cl4（H2O）]n（1） was prepared from a hydrothermal reaction and structurally characterized.Compound 1 crystallizes in the space group Fmmm of the orthorhombic system with eight formula units in a cell：a = 15.5165（4）,b = 17.5090（9）,c = 7.3318（5） ,V = 1991.9（2） 3,Cd4Cl4H2O7Se2,Mr = 863.38,Dc = 5.758 g/cm3,S = 1.075,μ（MoKα） = 16.820 mm-1,F（000） = 3088,R = 0.0427 and wR = 0.1220.Compound 1 features a 3-D structure with the cadmium atoms having two different coordination environments,i.e.,six-and eight-coordination geometries.Two different chain-like structures of cadmium-oxo polyhedra are interconnect to each other to give a 2-D layer of [Cd4（SeO3）2（H2O）]n4n＋.Between the [Cd4（SeO3）2（H2O）]n4n＋ layers is a novel chloride layer.A 3-D framework is constructed from these [Cd4（SeO3）2（H2O）]n4n＋ layers linked by the chloride layers.

Crystal Structure and Fluorescent Study of a Binuclear Europium(Ⅲ) Complex

A novel binuclear Eu（Ⅲ） complex [Eu2（dpa dioxide）2（NO3）4（bpdioxide）-（EtOH）] （dpa dioxide = di-2-pyridylamine N,N＇-dioxide, bpdioxide = 2,2＇-bipyridine N,N＇-dioxide） has been synthesized and it exhibits strong and sharp fluorescent emission at 614 nm under UV radiation of 245 nm at room temperature. X-ray structural determination indicates two independent Eu（Ⅲ） ions in the structure with different EuO8N and EuOgN environments. The compound crystallizes in the triclinic system, space group P1, with a = 10.8089（7）, b = 11.4670（8）, c = 17.1440（12） A, α = 92.834（2）, β = 93.854（3）, γ = 95.433（2）°, Z = 2, Dc = 1.876 g/cm3, V= 2107.3（2） A3, F（000） = 1168.0, the final R = 0.032 and wR = 0.086 for 6331 observed reflections with I 〉 2σ（I）.

Hydrothermal Synthesis, Crystal Structure and Photoluminescence of [Sm(PCA)_3(H_2O)_2]_n·6nH_2O

A new one-dimensional （1-D） compound [Sm（PCA）3（H2O）2]n·6nH2O （1, HPCA=pyrazinecarboxylic acid） has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the Pbca space group of orthorhombic system with a=19.465（3）, b=12.034（4）, c=19.842（4） , V=4648（2）3, C15H25N6O14Sm, Mr=663.76, Dc=1.897 g/cm3, S=1.023, μ（MoKα）=2.610 mm-1, F（000）=2648, R=0.0239 and wR=0.0616. Compound 1 is characteristic of an infinite 1-D chain-like structure with the samarium atoms locating at an environment of a monocapped square antiprism. The [Sm（PCA）3（H2O）2]n chains and the lattice water molecules interconnect together through π-π interactions and hydrogen bonding interactions to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title compound displays an emission in the greenish blue region.

Synthesis and Structure of a Novel Rare Earth Complex: Eu_3(dpa dioxide)_4·(CF_3COO)_5·H_2O

The novel europium complex Eu3（dpa dioxide）4·（CF3COO）5·H2O （dpa dioxide = di-2-pyridylamine N,N＇-dioxide） was prepared by the reaction of Eu（CF3CO2）3 with Dpa dioxide in acetonitrile under 95 ℃ and determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 41.632（8）, b = 14.662（3）, c = 23.300（4）A,β= 100.862（5）°, Z = 8, D = 1.775 g/cm^3, V = 13968（4）A^3, F（000） = 7232, the final R = 0.0464 and wR = 0.1168. In this tri-nuclear complex, each europium（Ⅲ） is nine-coordinated to adopt an unequal sphere geometry.

Synthesis, Structure and Photoluminescent Property of an Entangled Cd(Ⅱ) Complex Constructed from a Rigid Imidazolyl Ligand

The assembly of rigid 1, 4-di（1H-imidazol-4-yl）benzene （L） and Cd（OAc）2·2H2O affords an entangled complex [Cd（L）2（OAc）2]n （1） which was characterized by single-crystal X-ray diffraction, IR, elemental analysis and PXRD. The complex crystallizes in monoclinic, space group P21/c with a = 8.2603（9）, b = 11.8162（13）, c = 14.4138（16）, β = 105.309（2）o, V = 1356.9（3）3, Z = 2, C28H26CdN8O4, Mr = 650.97, Dc = 1.593 g/cm3, μ = 0.856 mm？1, S = 1.015, F（000） = 660, the final R = 0.0456 and wR = 0.1366 for 2532 observed reflections （I 2σ（I））. 1 possesses [Cd（L）2]n layer motifs, and parallel sets of layer motifs aggregate into a 2D ＋ 2D → 3D mutually interpenetrated system. Photoluminescence study revealed that complex 1 exhibits strong fluorescent emission bands in the solid state at room temperature.

Synthesis,Structure and Photoluminescence of (CH_3-4,4'-H_2bipy)-(HgCl_4) with CH_3-4,4'-H_2bipy Generated in Situ

A novel viologen（4,4＇bipyridinium）-based complex （CH3-4,4＇-H2bipy）（HgCl4） （1）,in which the CH3-4,4＇-H2bipy （MQ2＋） was generated in situ,has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group P21/c of monoclinic system with four formula units in a cell：a = 8.1848（6）,b = 21.809（2）,c = 9.0285（6） ,β = 107.377（1）°,V = 1538.0（2） 3,C11H11Cl4HgN2,Mr = 513.61,Dc = 2.218 g/cm3,S = 1.009,μ（MoKα） = 10.685 mm-1,F（000） = 956,R = 0.0360 and wR = 0.0812. The crystal structure analysis reveals that the title complex features an isolated structure based on a CH3-4,4＇-H2bipy moiety and a mercury atom terminally bound by four chlorine atoms. Photoluminescence investigation reveals a strong emission in blue region,which may originate from π→π＊ charge-transfer interaction of the CH3-4,4＇-H2bipy moiety.

Synthesis,Crystal Structure,and Photoluminescent and Semiconductive Properties of [La(C_6NO_2H_5)_3-(H_2O)_2]_(2n)·(nH_5O_2)(nHgCl_5)(2nHgCl_4)·(2nH_2O)

A new heterometallic 4f-5d inorganic-organic metal-isonicotinic acid complex [La（C6NO2Hs）3-（H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O） 1 has been synthesized via hydro- thermal reaction and structurally characterized. Complex 1 crystallizes in the space group C21c of monoclinic system with four formula units in a cell： a = 24.140（7）, b = 20.884（7）, c = 15.462（2）A, fl = 127.46（1）°, V = 6187（3）A3, C36HaTCl13Hg3La2N6020, Mr = 2224.24, Dc = 2.388 g/cm3, Z = 4, T = 293（2） K, μ（MoKa） = 9.401 mm-1, F（000） = 4160 and RIwR = 0.0376/0.0636 for 4130 observed reflections （I 〉 20（/）） and 5617 unique reflections. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in violet and orange regions. The luminescence spectra show stronger orange emission than violet emission. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap of 3.41 eV.

Synthesis and Crystal Structur of (4,4′-H_2bipy)[CdBr_4]·H_2O

The title compound （4,4＇-H2bipy）[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/1c with a = 8.260（3）, b = 23.926（7）, c = 9.774（2） A, β = 106.777（9）°, C10H12Br4CdN2O, M, = 608.26, V = 1849.4（9） A^3, Z = 4, Dc = 2.185 g/cm^3, S = 1.005, μ（MoKα） = 9.814 mm^-1, F（000） = 1128, R = 0.0646 and ωR = 0.0989. The crystal structure analysis of 1 reveals that the title compound features an isolated structure, based on discrete 4,4＇-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms.

Synthesis,Crystal Structure and Photoluminescence of [Gd(C_6NO_2H_5)_3-(H_2O)_2]_(2n)·(nH_5O_2)(nHgCl_5)(2nHgCl_4)·(2nH_2O)

A heterometallic 4f-5d inorganic-organic metaMsonicotinato hybrid [Gd（C6NO2H5）3- （H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O） 1 has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell： a = 24.234（8）, b = 20.816（7）, c = 15.333（3）A , β= 128.091（8）°, V = 6088（3）A^3, C36H47Cl13Gd2Hg3N6O20, Mr = 2260.92, Dc = 2.467 g/cm^3, S = 0.896, μ（MoKα） = 10.331 mm^-1, F（000） = 4216, R = 0.0344 and wR = 0.0629. The crystal structure analysis reveals that the title complex is characteristic of a one-dimensional chain-like structure. Photoluminescent investigation reveals that the title complex displays a broad and intense emission in the green region.

Synthesis and Structural Characterization of a Cyano-bridged 1-D Lanthanum(Ⅲ)-iron(Ⅲ) Complex [La(DMSO)_5(H_2O)](μ-CN)_2[Fe(CN)_4]·H_2O

ABSTRACT A new lanthanumm-ironm complex [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4]·H2O 1 （DMSO = dimethylsulfoxide） has been prepared by a facile approach, ball-milling method, and characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 9.7125（3）, b = 21.5336（7）, c = 14.3804（5）A, β = 93.242（3）°, C16H34FeLaN60O7S5, Mr= 777.55, V = 3002.8（2）A^3, Z = 4, Dc = 1.720 g/cm^3, S = 1.053, μ（MoKα） = 2.278 mm^-1, F（000） = 1564, R = 0.0490 and ωR = 0.1270. The crystal structure analysis of 1 reveals a slightly distorted squareantiprism eighffold-coordinated La（Ⅲ） ion and a 1-D zigzag chain structure extending through the Fe-CN-La-NC-Fe linkages. The [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4] species are held together via hydrogen bonds to form a three-dimensional framework.

[N-ethyl-4,4'-bipyridinium][ZnX_4](X = Cl or Br) with N-ethyl-4,4'-bipyridinium Generated In Situ:Syntheses, Structures, Fluorescence and TDDFT Calculations

Two new zinc bipyridinium compounds, [N-ethyl-4,4＂-bipyridinium][ZnX4] （X = CI （1） or Br （2）） with N-ethyl-4,4＂-bipyridinium generated in situ, have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction analyses. Both compounds are isostructural and crystallize in the P2/c space group of monoclinic system. Compound 1： a = 8.4397（5）, b = 21.988（1）, c = 8.8777（5） А, β = 106.490（1）°, V = 1579.7（2） A3, C2H15C14N2Zn, Mr = 394.43, Z = 4, Dc = 1.658 g/cm3, S = 1.068,/a（MoKa） = 2.218 mm-1, F（000） = 796, R = 0.0295 and wR = 0.0766. Compound 2： a = 8.4154（6）, b = 22.844（2）, c = 9.0308（7） A, fl = 106.026（1）°, V = 1668.6（2） A3, Cj/HjsBraN2Zn, Mr = 572.27, Z = 4, Dc = 2.278 g/cm3, S = 1.033, /l（MoKa） = 11.038 mm＂1, F（000） = 1084, R = 0.0427 and wR = 0.1175. Both of them are characteristic of an isolated structure with the zinc atoms locating at a tetrahedral environment. In both compounds, the N-ethyl-4,4＂-bipyridinium2＋ cations and ZnX42- anions interconnect together via hydrogen bonding interactions to construct a three-dimensional （3-D） supramolecular framework. Fluorescent studies reveal that both compounds exhibit a strong emission in the green region. In combination with the theoretical calculations, we can draw a conclusion that the emissions should result from ligand-to- ligand charge-transfer （LLCT） transition.

A New 3-D Lanthanide Porphyrin: Synthesis,Structure and Photophysical Properties

A new lanthanide porphyrin, [Smm（H3TPPSHI）]n-nH20 （1, H6TPPS = tetra（4- sulfonatophenyl）porphyrin）, has been synthesized through a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the P4/mcc space group of tetragonal system： a = 15.3683（12）, c = 9.895（2）/k, V = 2337.0（5） A3, C44H29N4OI3SaSm, Mr = 1100.30, Z = 2, Dc = 1.564 g/cm3, S = 1.063,μ（MoKa） = 1.502 mm-1, F（000） = 1102, R = 0.0583 and wR = 0.1666. Compound 1 is characteristic of a three-dimensional （3-D） framework with a slightly distorted square-antiprism eight-coordinated Sm3＋ ion. Fluorescent study revealed that compound 1 exhibits an emission in the red region. The fluorescence quantum yield and lifetime of 1 were determined to be 3.5% and 9.1 ns, respectively. UV-vis absorption spectra were also investigated.

Photoluminescent,Theoretical and X-ray Investigations on an Iron-nicotinato Cluster

An unprecedented oxo-centered, trinuclear iron nicotinato cluster, [Fe30o （C6NO2Hs）6（H20）3][Fe（H30）2C16]＇12H20＂6Br （1）, has been prepared via hydrothermal reac- tions and structurally characterized by X-ray diffraction. Compound 1 crystallizes in the R-3c space group of rhombohedral system with a = 21.763（4）, c = 24.361（3） A, V = 9992（3） A3, C36H66Br6C16Fe4N6030, Mr = 1978.51, De. = 11973 g/cms, S = 1.006,/（MoKa） = 4.778 mm-1, F（000） = 5880, Z = 6, R = 0.0591 and wR = 0.1054. The title complex features an isolated structure, based on one discrete [Fe30（C6NO2H5）6（H20）3]7＋ cation, one [Fe（H30）2C16]- anion, twelve lattice water molecules and six isolated bromine anions. These isolated moieties are interconnected via hydrogen bonds to yield a three-dimensional （3-D） supramolecular network. Photoluminescent investigation reveals that the title complex exhibits an emission in the purple region. Theoretical study reveals that the emission is attributed to the metal to ligand charge-transfer （MLCT） interaction.

Crystallographic Characterization of Lu_(2)O@C_(s)(6)-C_(82)and Er_(2)O@C_(s)(6)-C_(82):The Role of Metal Species on Cluster Configuration

Comprehensive Summary Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes.However,how the internal metal species interplay with the cluster configuration inside oxide clusterfullerenes remains poorly understood.Herein,we successfully captured two oxide clusterfullerenes with different metals,namely,Lu_(2)O@C_(82)and Er_(2)O@C_(82),to elucidate the role of metal species in tuning cluster configuration.The two molecules have been fully characterized by mass spectrometry,Vis-NIR absorption spectroscopy,cyclic voltammetry,and single-crystal X-ray diffraction.

Structure and Photophysical Properties of an Upconversion Holmium-mercury Compound with a 2-D Layer-like Motif

Using a hydrothermal reaction,a novel holmium-mercury compound{[Ho(IA)(HIA)_(2)(H2 O)_(2)]_(2-)(Hg_(3)Br_(8))}n(nHgBr_(2))·2 nNO_(3)(1,HIA is isonicotinc acid)was synthesized and its crystal structure was characterized by single-crystal X-ray diffraction.Compound 1 crystallizes in monoclinic system,space group P2/c with a=13.0647(6),b=9.4659(3),c=26.0832(14)Å,β=97.522(4)°,V=3197.9(2)Å^(3),C_(36)H_(36)Br_(10)Hg_(4)Ho_(2)N_(8)O_(22),M_(r)=2863.95,Z=2,D_(c)=2.974 g/cm^(3),μ(Mo Kα)=18.331 mm^(–1) and F(000)=2575.It displays a two-dimensional(2 D)layer-like structure.A solid-state photoluminescence experiment revealed that it shows upconversion green emission.The emission peaks should come from the ^(5)I_(8)→^(5)G_(6) and ^(5)S_(2)→^(5)I_(8) characteristic emission of the 4 f electrons of the Ho3+ion.Compound 1 has a CIE chromaticity coordinate(0.1774,0.526).A solid-state UV-visible diffuse reflectance spectrum unveiled that this compound has a wide optical band gap of 3.26 eV.

Hydrothermal Preparation, Crystal Structure and Properties of {[ZnTCPP（EtOH）][Zn（en）]2}n（EtOH）2n with a Novel Two-Dimensional （2-D） Motif

A novel zinc porphyrin, {[ZnTCPP（EtOH）][Zn（en）]2},（EtOH）2, （1） （TCPP=meso-tetra（4-carboxyphenyl）- porphyrin; EtOH=ethanol; en=ethylenediamine） was obtained via a hydrothermal reaction and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the space group C2/c of the monoclinie system with eight formula units in a cell： a=32.465（4） A, b=10.527（3） A, c=31.845（3） A,β=95.524（6）°, V=10832（4） A3, C58H57NsOaIZn3, Mr= 1238.23, Dc= 1.518 g/cm3, S=1.005, μ（Mo Kα）= 1.388 mm-1, F（000）=5112, R=0.0650 and wR=0.1574. Complex 1 features a novel 2-D layered motif. The spectral data of UV-vis, FT-IR and fluorescence are reported.