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Fluorescence emission modulation in cyanido-bridged Fe(Ⅱ)spin crossover coordination polymers

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Science China Chemistry 2022年第8期65卷 1569-1576页

作者： Xue-Ru Wu Zhi-Kun Liu Min Zeng Ming-Xing Chen Jun Tao Shu-Qi Wu Hui-Zhong Kou Department of Chemistry Tsinghua UniversityBeijing 100084China Key Laboratory of Cluster Science of Ministry of Education School of Chemistry and Chemical EngineeringLiangxiang CampusBeijing Institute of TechnologyBeijing 102488China Analytical Instrumentation Center College of Chemistry and Molecular EngineeringPeking UniversityBeijing 100871China Institute for Materials Chemistry and Engineering&IRCCS Kyushu University744 MotookaNishi-kuFukuoka 819-0395Japan

Synergistic fluorescent spin crossover(SCO)bifunctional molecular materials have novel applications in the molecule-based magneto-optical ***,we report two novel three-dimensional(3D)Hofmann-type fluorescent SCO complexes[Fe^(II)-(tppe)MI(CN)_(2)]ClO_(4)·nSolv(tppe=tetra-(4-pyridylphenyl)ethene,M=Ag(tppe-Ag),Au(tppe-Au)).Both complexes show one-step abrupt SCO with the transition temperature of 230 K for tppe-Ag,and 245 K for tppe-Au accompanied by a color change from red to light *** SCO process is confirmed by the variable-temperature single-crystal X-ray diffraction analysis on *** the first time,the abnormal increase in emission intensity and concomitant large bathochromic shifts in the fluorescence spectra during the SCO process are realized in the 3D Hofmann-type coordination polymers expanded by the tetradentate tppe ***,tppe-Ag exhibits the unprecedented fluorescence emission from green to the edge of yellow.

关键词： fluorescence spin crossover multifunctional materials coordination polymers synergetic effect

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Novel lanthanide coordination polymers based on mixed N,O-donor ligands and their visible-light-driven photocatalytic performance

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Journal of Rare Earths 2023年第1期41卷 85-90页

作者： Jun Chen Weizhi Kou Shunsheng He Chenlan Lin Xin Wang Lianshe Fu Ting-Hai Yang Jiangsu Laboratory of Precious Metals Processing Technology and Application School of Chemistry&Environmental EngineeringJiangsu University of TechnologyChangzhou 213001China Department of Physics CICECO-Aveiro Institute of MaterialsUniversity of Aveiro3810-193AveiroPortugal

In the present work,we prepared three isostructural lanthanide(Ln) coordination polymers(CPs).namely [Ln(Hhpc)(phen)(NO_(3))](Ln=Gd(1),La(2),Y(3),H_(3)hpc=5-hydroxy-1 H-pyrazole-3-carboxyIic acid,phen=1,10-phenanthroline) by hydrothermal *** structures were characterized by single crystal X-ray diffraction,Fourier transform infrared spectrum,elemental analysis,powder X-ray diffraction and thermal gravimetric *** 1-3 are isostrutural and exhibit two-dimensional(2 D)wavy layered structure constructed from inorganic chains,in which equivalent eight coordinated Ln^(3+) ions are linked through carboxylate *** three dimensional supramolecular structure is further formed by hydrogen *** photocatalytic experiments show that CPs 2 and 3 exhibit good photocatalytic performances under visible light in degradation of methylene blue organic *** photocatalytic degradation efficiencies in 90 min are about 86.19% and 93.60% for CPs 2 and 3,*** photocatalytic degradation mechanisms have been proposed through photoelectrochemical and trapping radical experiments.

关键词： Lanthanides coordination polymers Photocatalytic degradation Pyrazole carboxylic acid Rare earths

Tetraolefin stereospecific photodimerization and photopolymerization in coordination polymers

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Science China Chemistry 2022年第10期65卷 1867-1872页

作者： Wei-Jie Gong Zhan-Yong Yang Yu-Xuan Hong Dong Liu Zheng Niu Pierre Braunstein Jian-Ping Lang College of Chemistry Chemical Engineering and Materials ScienceSoochow UniversitySuzhou 215123China State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials School of Chemistry and Chemical EngineeringHuaiyin Normal UniversityHuaian 223300China Universitéde Strasbourg-CNRS Institut de Chimie(UMR 7177 CNRS)4 rue Blaise Pascal-CS 90032Strasbourg 67081France

In the context of the highly desirable design and preparation of smart materials with adjustable properties based on photoreactive compounds,we report two unique photoreactive coordination polymers(CPs),{[Zn(4-Iba)_(2)(4-tkpvb)]·H_()2O}_(n)(1,4-HIba=4-iodobenzoic acid,4-tkpvb=1,2,4,5-tetrakis(4-pyridylvinyl)benzene)and[Cd(1,4-bdc)(4-tkpvb)]_(n)(2,1,4-H_(2)bdc=1,4-benzenedicarboxylic acid).Depending on the metal ions and auxiliary carboxylate ligands used,the 4-tkpvb ligands in 1 and 2 adopt different mutual arrangements,which facilitate the photodimerization and photopolymerization reactions in single crystal to single crystal(SCSC)*** UV light irradiation which results in the dimerization of the 4-tkpvb ligands,the one-dimensional(1D)zigzag chainsof 1 are transformed into a two-dimensional(2D)network of{[Zn(4-Iba)_(2)(bpbtpvcb)_(0.5)]·H_(2)O}_(n)(1a,bpbtpvcb=1,3-bis(4-pyridyl)-2,4-bis(2,4,5-tri(2-(4-pyridyl)vinyl)phenylcyclobutane).Similarly,in the crystals of 2,all 4-tkpvb ligands experience a photopolymerization reaction to form an unprecedented 1D linear organic polymer,poly-1,3-bis(4-pyridyl)-2,5-bis(2-(4-pyridyl)-vinyl)phenyl)cyclobutane(poly-bpbpvpcb).Furthermore,the 2D network of 2 is converted into a three-dimensional(3D)framework of[Cd_(n)(1,4-bdc)_(n)(poly-bpbpvpcb)](2a).This work not only offers a new protocol to selectively synthesize new supramolecular cyclic compounds,but also expands the application of photopolymerization to the synthesis of macromolecules.

关键词： coordination polymers single-crystal to single-crystal transformation photodimerization photopolymerization cycloaddition

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Syntheses and Crystal Structures of Two One-dimensional coordination polymers Constructed from a Flexible Hinge-like Ligand

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Chinese Journal of Structural Chemistry 2008年第12期27卷 1465-1468页

作者：韩磊周燕赵文娜 State Key Laboratory Base of Novel Functional Materials & Preparation Science Faculty of Materials Science & Chemical EngineeringNinbo University Key Laboratory for Molecular Design and Nutrition Engineering of Ningbo Ningbo Institute of TechnologyZhejiang University

By using the flexible hinge-like ligand 2,2＇-bis（3-hydroxy-l,4-naphthoquinone）（H2bhnq）, two isomorphous one-dimensional zigzag chain coordination polymers have been obtained. Single-crystal X-ray analyses revealed that the metal centers in these two complexes are distorted octahedra involving four oxygen atoms of two bhnq2 anions, and two oxygen atoms of two DMF molecules situated in trans positions to one another. Crystal data for [Mn（bhnq）（DMF）2]n 1： C26H22MnN2O8, Mr = 545.40, monoclinic, space group C2/c, a = 14.936（3）, b = 10.362（2）, c = 15.901（3）A., β = 99.86（3）°, V = 2424.7（8）A3, Z = 4, Dc = 1.494 g/cm^3, F（000） = 1124,μ = 0.599 mm^-1, final GOOF = 1.025, R = 0.0654 and wR = 0.1537. Crystal data for [Cd（bhnq）（DMF）2]n 2： C26H22CdN2O8, Mr = 602.86, monoclinic, space group C2/c, a = 14.839（3）, b = 10.493（2）, c = 16.034（3）A, β = 99.40（3）°, V = 2463.1（9）A^3, Z = 4, Dc = 1.626 g/cm^3, F（000） = 1216,μ = 0.941 mm^-1, final GOOF = 1.069, R = 0.0358 and wR = 0.0944.

关键词： coordination polymers crystal structures zigzag chains 2,2'-bis(3-hydroxy-1,4-naphthoquinone)

Syntheses and Crystal Structures of Two Co(II) coordination polymers with 4,4'-(Hexafluoroisopropylidene)bis(benzoic acid)

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Chinese Journal of Structural Chemistry 2008年第11期27卷 1305-1310页

作者：周燕韩磊 State Key Laboratory Base of Novel Functional Materials & Preparation Science Faculty of Materials Science & Chemical EngineeringNingbo University

Two new one-dimensional zigzag chain coordination polymers, [Co（hfipbb）（2,2＇- bpy）（H2O）2]n 1 and [Co（hfipbb）（1,10-phen）（H2O）], 2, have been synthesized under hydrother- mal reactions from COCl2.6H20, 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid） and 2,2＇ -bipyridine or 1,10-phenanthroline ligands, respectively. Single-crystal X-ray analyses revealed that the zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O-H…O hydrogen-bonds and π…π stacking interactions. Crystal data for 1： CzTHajCoF6N2Os Mr = 641.38, orthorhombic, space group Pnna, a = 9.3820（19）, b = 27.366（6）, c = 10.106（2）A, V = 2594.8（9）A3, Z = 4, Dc = 1.642 g/cm3, F（000） = 1300,/t = 0.752 mm-l, R = 0.0311 and wR = 0.0924. Crystal data for 2： C29H18CoF6N2O5, Mr = 647.38, monoclinic, space group P21/n, a = 7.7626（16）, b = 29.446（6）, c = 11.281（2）A,β= 93.98（3）°, V= 2572.3（9）A3, Z = 4, Dc = 1.672 g/cm3, F（000） = 1308,μ= 0.757 mm-1, R = 0.0403 and wR = 0.0820.

关键词： coordination polymers crystal structures zigzag chains 4,4'.(hexafluoroisopro- pylidene)bis(benzoie acid)

From Chain to Layer Structure: Zn^(II) coordination polymers Derived from Diphenic Acid

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Chinese Journal of Structural Chemistry 2005年第9期24卷 1007-1016页

作者：王瑞虎弓亚琼韩磊袁大强洪茂椿 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 of the Chinese Academy of Sciences Beijing 100039 China State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter The Chinese Academy of Sciences Fuzhou Fujian 350002 China

Three Zn^Ⅱ coordination polymers, [Zn（py）（H2O）（dpa）]n 1, [Zn2（4,4’-bipy）2（dpa）2]n 2 and [Zn（bpe）（H2O）2（Hdpa）2]n 3 （py=pyridine, H2dpa=diphenic acid, 4,4＇-bipy-4,4＇-bipyridine, bpe = 1,2-bis（4-pyridyl）ethane）, were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in monoclinic, space group C2/c with a = 23.014（3）, b = 8.7184（13）, c = 18.091（3）A° ,8 = 95.964（3）°, V=3610.2（9）A°^3, Z=8, C19H15NO5Zn, Mr=402.69, Dc=1.482 g/cm^3, F（000）=1648, μ（MoKa）=1.389 mm^-1 the final R=0.0431 and wR = 0.1120 for 4239 observed reflections with 1〉2σ（I）. 2 crystallizes in orthorhombic, space group Fddd with a=23.1613（5）, b=24.0324（6）, c=29.4785（1）A°, V= 16408.4（5） A°3, Z=32, C24H16N2O4Zn, Mr=461.76, Dc=1.495 g/cm^3, F（000）=7552, μ（MoKa）=1.232 mm^-1, the final R=0.0542 and wR=0.1724 for 3632 observed reflections with 1〉2σ（I）. 3 crystallizes in orthorhombic, space group C2/c with a=19.142（4）, b = 13.862（3）, c = 15.625（3） A°,β=122.404（3）°, V= 3500.3（11）A°^3, Z=8, C2oHiTNO5Zn0.50, Mr=384.03, Dc=1.457 g/cm^3,F（000）=1592,μ（MoKα）=0.766 mm^-1, the final R=0.0400 and wR=0.1210 for 4024 observed reflections with I 〉 2σ（I）.

关键词： diphenic acid zinc coordination polymers crystal structure

Synthesis of energetic coordination polymers based on 4-nitropyrazole by solid-melt crystallization in non-ionization condition

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Defence Technology（防务技术） 2023年第10期28卷 13-22页

作者： Ting-wei Wang Shu Bu Kun Wang Lu Zhang Zhen-xin Yi Shun-guan Zhu Jian-guo Zhang State Key Laboratory of Explosion Science and Technology Beijing Institute of TechnologyBeijing100081China School of Chemical Engineering Nanjing University of Science and Technology200 Xiaolingwei StreetXuanwuNanjing210094China Department of Chemistry Laboratory of Structure and Functional Regulation of Hybrid MaterialsAnhui UniversityMinistry of EducationHefei230601China

Based on the theory of crystallization,a solvent-free solid-liquid phase crystallization method called solid-melt crystallization was designed to prepare energetic coordination *** target compounds[Cu(NPyz)_(4)NO_(3)]·NO_(3)(ECPs-1)and Cu(NPyz)_(4)(ClO_(4))_(2)(ECCs-2)were prepared through programmed heating and cooling by using 4-nitropyrazole(NPyz),(Cu(NO_(3))_(2)·5H_(2)O and Cu(ClO_(4))_(2)·5H_(2)O) as raw *** addition,crystallization pre-experiments and annealing experiments also verified the feasibility of the *** structures were confirmed by IR,elemental analysis,single-crystal X-ray diffraction and powder X-ray *** physicochemical properties and sensitivity test results showed that ECCs-2 has better thermal stability(T_(d)=221℃),while ECPs-1 is less sensitive to mechanical stimuli(IS=12 J,FS=240 N).Calculations based on EXPLO5 and the Kamlet-Jacobs equation showed that ECCs-2 has more considerable detonation performance(P=25.2 GPa,D=7.5 km/s).In comparison,the more intuitive results from the HN test,flame test,thermal resistance test and lead plate explosion test revealed that ECCs-2 has an“acceptable”detonation *** laser detonation test also showed that ECCs-2 is a promising excellent laser detonation material(E=408 mJ,P=24 W,τ=17 ms).

关键词： 4-Amino-1,2,5-oxadiazole-3-carbohydrazide Crystallization coordination polymers Laser Primary explosives

Two-dimensional bimetallic coordination polymers as bifunctional evolved electrocatalysts for enhanced oxygen evolution reaction and urea oxidation reaction

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Journal of Energy Chemistry 2021年第12期30卷 230-238,I0005页

作者： Qiang Li Lele Lu Jingwei Liu Wei Shi Peng Cheng Key Laboratory of Advanced Energy Materials Chemistry(MOE) College of ChemistryNankai UniversityTianjin 300071China

Two-dimensional coordination polymers(CPs) have aroused tremendous interest as electrocatalysts because the catalytic performance could be fine-tuned by their well-designed coordination layers with highly accessible and active metal ***,it remains great challenge for CP-based catalysts to be utilized for electrocatalytic oxidation reactions due to their inefficient activities and low catalytic ***,we applied a mixed-metal strategy to fabricate two-dimensional Co_xNi_(1-x)-CPs with dual active sites for electrocatalytic water and urea *** metal ratio regulation in the twodimensional layer,an optimized Co_(2/3)Ni_(1/3)-CP exhibits a water oxidation performance with an overpotential of 325 mV at a current density of 10 mA cm^(-2) and a Tafel slope of 86 mV dec^(-1) in alkaline solution for oxygen evolution ***,a lower potential than that of commercial RuO_(2) is observed over20 mA cm^(-2).Co_(2/3)Ni_(1/3)-CP also displays a potential of 1.381 V at 10 mA cm^(-2) for urea oxidation reaction and a Tafel slope of 124 mV dec^(-1).This mixed-metal strategy to maximize synergistic effect of different metal centers may ultimately lead to promising electrocatalysts for small molecule oxidation reaction.

关键词： coordination polymers Electrocatalysis Oxygen Evolution Reaction Urea Oxidation Reaction

Application of three Ln(Ⅲ)-coordination polymers in fields of luminescence,antibacteria and detection of Fe^(3+) and 4-nitrophenol

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Journal of Rare Earths 2023年第9期41卷 1392-1397,I0005页

作者： Lun Zhao Yue Han Guanlin Guo Helong Bai Zhexin Wang Hongwei Jing Guanying Song Ziyun Wang Jiayu Li Jia Li College of Chemistry Changchun Normal UniversityChangchun 130032China

Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La_(2)(L)_(3)(DMF)(H_(2)O)_(3)]·H_(2)O}_n(1),{[Eu_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·(H_(2)O)}_n(2){Tb_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·H_(2)O}n(3) were successfully synthesized from H_(2)L(N,N'-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to *** the concentration of 4-nitrophenol reaches 5.98 × 10^(-3) mmol/L,the fluorescence intensity of compound 3 is quenched by 59%.The calculated K_(SV) is 7.56 × 10~4 and limit of detection(LOD) is 4.73 μg/L.3 exhibits a highly sensitive detection towards Fe^(3+) and compound 2 shows outstanding antibacterial effects on Staphylococcus aureus,re *** white light emission was also investigated by changing the mixing ratio of LaNO_(3),EuNO_(3) and TbNO_(3) during the preparation of coordination polymers.

关键词： coordination polymers Lanthanide-based Detection Luminescence Antibacterial Rare earths