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Salt-inclusion chalcogenides:Double functional moieties design strategy toward excellent nonlinear optical materials

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Chinese Journal of Structural Chemistry 2023年第3期42卷 24-34页

作者： Chao-Hong Xie Bin-Wen Liu guo-cong guo State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian350002People's Republic of China University of Chinese Academy of Sciences Beijing100190People's Republic of China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China FuzhouFujian350108People's Republic of China

Nonlinear optical(NLO)material are of great importance in converting the frequency to extend the laser spectrum in mid-and far-infrared(IR)regions where lasers operate poorly or are ***,the contradiction between large second-harmonic generation(SHG)intensity and wide band gap(E_(g))is a long-standing problem for IR NLO *** address the issue,metal chalcogenides have been successfully synthesized and developed excellent optical properties in the past few *** a newly discovered category of chalcogenides,salt-inclusion chalcogenides with distinctive structures and brilliant performances have been placed great expecta-tions to be a novel *** this review,52 compounds in this thriving family are categorized via dimensions of host and guest parts,further discussing the relationships between their structures and NLO properties,as well as future perspectives of this family.

关键词： Salt-inclusion chalcogenide Nonlinear optical material Host and guest parts Structural crystal

Synthesis,Crystal Structure and Fluorescent Properties of New Layered Thiophosphate Cs_(2)Ga_(3)PS_(8)

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Chinese Journal of Structural Chemistry 2021年第10期40卷 1271-1276页

作者： CHEN Wen-Fa LIU Bin-Wen JIANG Xiao-Ming guo guo-cong State Key Laboratory of Structural Chemistiy Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China University of Chinese Academy of Sciences Beijing 100190China

A new quaternary metal thiophosphate,Cs_(2)Ga_(3)PS_(8),in triclinic P1^(-) space group has been successfully synthesized by a reactive-flux *** structural framework is derived from well-known AM^(Ⅲ)M^(Ⅳ)Q_(4) (A=alkali metal;M^(Ⅲ)=Al,Ga,In;M^(Ⅳ)=Si,Ge,Sn;Q=S,Se) system and composed of two-dimensional ^(2)∞[Ga_(3)PS_(8)]^(2-) layers separated by Cs^(+).The compound exhibits a wide band gap of 3.08 eV and congruent-melting behavior with melt point of 645℃.Interestingly,Cs_(2)Ga_(3)PS_(8) exhibits a broad photoluminescent emission band at 420 nm upon excitation at 295 ***,electronic structure calculations indicate that Cs_(2)Ga_(3)PS_(8) is a direct band gap compound and its luminescent process can be mainly ascribed to electron transfer from the S-3p and Ga-4p states to S-3p and P-3p.

关键词： chalcogenide thiophosphate crystal structure solid-state phase synthesis

Synthesis and Structural Characterization of a New Cadmium(II) Complex with a Double Betaine

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Chinese Journal of Structural Chemistry 2005年第8期24卷 940-944页

作者： ZHENG Fa-Kun WU A-Qing LI Yan guo guo-cong HUANG Jin-Shun State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter The Chinese Academy of Sciences Fuzhou Fujian 350002 China Graduate School The Chinese Academy of Sciences Beijing 100039 China

A new flexible double betaine L （L = 1,4-bis（pyridinio-4-carboxylato-N-methyl）benzene, C20H16N2O4） and its cadmium（Ⅱ） complex [Cd（H2O）aL（NO3）]NO3.H2O 1 were synthesized. Complex 1 was obtained by self-assembly reaction of [Cd（NO3）2]-4H2O and L in hot water,and its crystal structure was determined by single-crystal X-ray diffraction analysis. Crystallographic data for complex 1： C20H24CdN4O14.H2O, Mr = 674.85, monoclinic, space group P21/c, a =13.7854（3）, b = 14.2820（3）, c = 14.9188（4） ,A°, β = 116.418（1）°, V = 2630.5（1）A°^3, Z = 4, Dc= 1.704g/cm^3,/J（MoKα） = 0.911 mm^-1, F（000） = 1368, the final R = 0.0315 and wR = 0.0768 for 3637 observed reflections with I 〉 2σ（I）. In complex 1, L acts as a monodentate ligand to link a Cd（Ⅱ） ion in a novel coordination mode of double betaines. The mononuclear [Cd（H2O）aL（NO3）] units are connected through intermolecular hydrogen bonds and π-π stacking reactions to generate a 3D network.

关键词： cadmium(Ⅱ) complex crystal structure double betaine hydrogen bonds

Synthesis and Crystal Structure of a New Lanthanum(III) 4-Cyanobenzoate Complex

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Chinese Journal of Structural Chemistry 2007年第5期26卷 575-579页

作者： LI guo-Qing LI Yanb ZOU Wen-Qiang CHEN Qi-Yong ZHENG Fa-Kun guo guo-cong Chemistry and Life Science School Quanzhou Normal University Quanzhou Fujian 362000 China State Key Laboratory of Structural Chemistry Fujian Institute of Research on theStructure of Matter The Chinese Academy of Sciences Fuzhou Fujian 350002 China Graduate School of the Chinese Academy of Sciences Beijing 100039 China

A new dinuclear La（Ⅲ） complex [La2（4-cba）4[H（4-cba）2]2（phen）2（H2O）4] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by singlecrystal X-ray diffraction. Crystallographic data： C88H58La2N12O20, Mr = 1881.28, triclinic P1, a = 7.518（3）, b = 17.033（6）, c = 17.551（6）A, α = 115.333（4）, β = 92.9910（10）, γ = 99.366（5）°, V = 1985.3（12）A^3, Z = 1, Dc = 1.574 g/cm^3, F（000） = 944 μ = 1.145 mm^–1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with Ⅰ 〉 2σ（I）. In 1, two nine-coordinated La（Ⅲ） ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La（Ⅲ） ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.

关键词： lanthanum(Ⅲ) complex 4-cyanobenzoic acid crystal structure hydrogen bonds

Highly crystallization-induced emissive luminophores with mechanoluminescent features for two-photon harvesting fluorescence imaging and latent fingerprint identification

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Nano Research 2024年第7期17卷 6475-6482页

作者： Jian Lu Juan Gao Rui-Xuan Qian Shuai-Hua Wang Fa-Kun Zheng guo-cong guo Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou 350108China State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China

Fluorescence imaging can be employed in fields of medical treatment,astronomical exploration,and national defense *** fluorescence imaging often takes the single-photon techniques,which is vulnerable to background interference and ***,two-photon fluorescence imaging can achieve much higher-resolution fluorescence imaging for reducing scattering and deeper ***,by assembling the tetraphenylethylene backbones with nontoxic and non-noble K^(+)ions,compound 1([(Hdma)K(H_(2)ettc)]_(n),H_(4)ettc=4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'-biphenyl]-4-carboxylic acid)))with the crystallization-induced emissions exhibited charming fluorescence imaging under two-photon excitation microscopy(TPEM).Besides,luminescent powders based on compound 1 can achieve high-resolution fingerprint recognition,providing secure access control and identification for a novel authentication *** with the commercial fluorescent dyes coumarin-6,the as-synthesized compound 1 showed great solvent stability,indicating its durability against harsh ***,compound 1 shows mechanoluminescent properties for the perturbation of weak supramolecular interactions within ordered arrangements of the H_(2)ettc^(2−)*** novel compound has provided an important insight to the development of twophoton fluorescence imaging and advanced external-stimuli responsive materials.

关键词： crystallization-induced emission fluorescence imaging two-photon absorption fingerprint recognition mechanoluminescence

High-Performance RuCl3 Catalyst Systems for Hydro-Esterification of Methyl Formate and Ethylene

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Chinese Journal of Chemistry 2019年第8期37卷 769-774页

作者： Yan-Ru Li Zhong-Ning Xu Bing Bai Zhi-Qiao Wang guo-cong guo State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian 350002China University of Chinese Academy of Sciences Beijing 100049China School of Physical Science and Technology ShanghaiTech UniversityShanghai 201210China Shanghai Institute of Ceramics Chinese Academy of SciencesShanghai 200050China

Summary of main observation and conclusion RuCl3 catalyst system has many advantages for the hydro-esterification of methyl formate and ethylene to methyl ***,the unsatisfied performance restricts the development of this *** this work,high-performance RuCl3 catalyst systems (RuCl3-[PPN]Cl-Et4NI and RuCl3-Nal) are firstly reported for this *** RuCl3-[PPN]Cl-Et4NI catalyst system,the conversion of methyl formate and the selectivity to methyl propionate are 93.9% and 90.9% at mild reaction conditions (165 ℃,2.5 MPa),***,a simple inorganic RuCl3-Nal catalyst system achieves 88.8% conversion of methyl formate and 97.6% selectivity to methyl propionate (86.7% yield) at same ***,as a promoter,may inhibit the decomposition of methyl formate and be conducive to the formation of methyl *** effects of solvents and promoters are investigated in *** addition,the reaction mechanism has been also *** is hoped to lay a certain foundation for further industrial application.

关键词： RuCl3 Catalyst Systems Hydro-Esterification Methyl Formate Ethylene

Synthesis, Single-crystal Structure, and Optical and Magnetic Properties of CaEr_2S_4

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Chinese Journal of Structural Chemistry 2007年第8期26卷 973-979页

作者： ZENG Hui-Yi Mattausch Hansjtirgen ZHENG Fa-Kun DONG Zhen-Chao guo guo-cong HUANG Jin-Shun State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter The Chinese Academy of Sciences Fuzhou Fujian 350002 China Max Planck Institute for Solid State Research Heisenbergstrasse 1 D-70569 Stuttgart Germany Hefei National Laboratory for Physical Sciences at Microscale University of Science and Technology of China Hefei Anhui 230026 China

Brown needle-like crystals of CaEr2S4 were isolated as the major product from a reaction of elements and binary sulfides by a two-step flux technique. CaEr2S4 crystallizes in the orthorhombic space group Pnma with a=12.845（4）, b=3.862（4）, c=13.001（2）（A）, V=645.0（7）（A）3,Z=4, F（000）=880,μ（MoKα）=27.794 mm^-1, the final R=0.0528 and wR=0.0562 for 1070observed reflections with I 〉 3σ（I）. The CaEr2S4 structure forms a three-dimensional framework that consists of interconnected tetra-octahedral Er4S18 fragments. Ca^2＋cations, in a monocapped trigonal prism geometry, are stuffed in two parallel rows into the one-dimensional channels along the b direction. CaEr2S4 is an infrared-transparent semiconductor with a band gap of 1.81 eV. Magnetic susceptibility measurements over 6～300 K indicate a Curie-Weiss paramagnetic behavior for the phase, with an effective magnetic moment of 9.64（1） μB per Er^3＋ ion.

关键词： rare-earth chalcogenides flux crystal growth crystal structure optical and magnetic properties

Visible Light-induced Photoluminescence of a Zinc(Ⅱ) Complex of N-methyl-4,4-bipyridinium Cation

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Chinese Journal of Structural Chemistry 2019年第2期38卷 317-324,169页

作者： DU Ming-Xiu YANG Chen CAI Li-Zhen guo guo-cong State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences

Compounds with visible-light-induced photoluminescence are particularly attractive in acting as the emitting components of light-emitting diodes and fluorescent probes for biological applications. A new complex [Zn(NCS)_3(MQ)](MQ^+ = N-methyl-4,4?-bipyridinium) with an isolated molecular structure has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and solid-state photoluminescent determination. Crystal data: C_(14)H_(11)N_5S_3Zn, M_r = 410.83, monoclinic, space group P2_1/c, a = 8.809(5), b = 13.138(7), c = 15.580(9) ?, b = 104.433(10)°, V = 1746.2(17) ?~3, Z = 4, D–c = 1.563 g×cm^3, μ = 1.769 mm^(–1), F(000) = 832, the final R = 0.0376 and wR = 0.1243 for 2850 observed reflections with I > 2s(I). In the crystal structure, the zinc atom is tetrahedrally coordinated by one MQ+ ligand and three NCS– groups to yield a tetrahedral configuration. The bond length of Zn–NMQ is clearly shorter than those found in reported Zn(Ⅱ) complexes of 4,4?-bipy. The isolated units are joined by C–H···S interactions to generate a 2D hydrogen-bonding network. This compound displays visible light-induced photoluminescence, which originates from both intraligand charge-transfer of the MQ+ ligand and NCS~–→MQ^+ charge-transfer according to a density of states(DOS) calculation. Moreover, its emission band shows a clear blue shift compared with those of halide compounds.

关键词： zinc complex N-methyl-4 4-bipyridinium photoluminescence visible-light excitation

Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

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Chinese Journal of Structural Chemistry 2005年第11期24卷 1281-1285页

作者： LI Yan WU A-Qing ZHENG Fa-Kun guo guo-cong LU Can-Zhong HUANG Jin-Shun State Key Laboratory of Structural Chemistry Fujian Institute of Research on theStructure of Matter The Chinese Academy of Sciences Fuzhou Fujian 350002 China Graduate School The Chinese Academy of Sciences Beijing 100039 China

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3）（4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

关键词： copper(Ⅱ) complex,4-cyanobenzoic acid crystal structure hydrogen bonds,π-π stacking