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Three new MOFs with unusual Cu_6~Ⅱcluster, linear Cu~Ⅱ chain and triangular Cu_3~Ⅱcore motifs tuned by sulfonate group: Synthesis, structures and magnetic properties

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Science China chemistry 2013年第4期56卷 465-474页

作者： YANG EnCui WANG XiuGuang ZHANG CuiHua YANG Na LIU ZhongYi ZHAO XiaoJun Tianjin key laboratory of Structure and Performance for functional Molecules key laboratory of inorganic-Organic Hybrid functional material chemistry Ministry of Education College of chemistry Tianjin Normal University

Three new MOFs with the same components but different structures and magnetic behavior, {[Cu6（atr）6（H20）2（,u3- OH）2（SOa）5]＇5.25H20}n （1）, {[Cu2（atr）2（,t/-OH）2（SOa）].3H20}n （2）, and {[CuT（atr）6（H20）6（fl3-OH）2（SOn）6].2H20}n （3）（atr= 4-amino-l,2,4-triazole）, were respectively synthesized by diffusion reactions in the presence of different structure-directing agents. Complex 1 is a slightly spin-frustrated antiferromagnetic layer with sulfonate aggregated Cun6 clusters periodically ex- tended by ditopic sulfonate linkers. 2 is a grid-based coplanar sheet with hydroxyl group bridged -CuOCu- linear-chain inter- linked by pairs of p3-atr ligands, exhibiting strong antiferromagnetic interactions to lead to an S = 0 spin ground state at low temperature. In contrast, air-instable 3 has a ladder-like broad-ribbon structure constructed from triangular CuII3 cores and cen- trosymmetric CuII1 octahedra. Obviously, the variable Cun-ligand connectivity and the involving magnetic properties are sig- nificantly dominated by the cooperative and variable binding modes of the mixed sulfonate-atr ligands and bi-/tridentate bridging hydroxyl heterobridges.

关键词： 4-amino-l,2,4-triazole polynuclear metal cluster magnetism spin frustration

A Novel Three-dimensional Triazole-based Zinc(Ⅱ) Coordination Polymer Controlled by the Spacers of Dicarboxylate Ligand with(4~2,6~2,8~2)(4,6~2,8~3) Topology

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Chinese Journal of Structural chemistry 2019年第9期38卷 1571-1577页

作者： ZHENG Chao-Yang YANG Han-Wen WANG Jia-Duo MAN Ting-Li ZHAO Zi-Bo ZHAO Hong-Kun WANG Xiu-Guang YANG En-Cui College of chemistry Key Laboratory of Inorganic-organic Hybrid Functional Material Chemistry Ministry of Education Tianjin Key Laboratory of Structure and Performance for Functional Molecules Tianjin Normal University

A novel mixed-ligand coordination polymer [Zn(BTA)(ip)0.5]n(1, HBTA = benzotriazole, H2 ip = isophthalic acid) has been synthesized under hydrothermal conditions, which was further characterized by X-ray diffraction, IR spectrum, elemental analysis and TG-DTA experiments. Complex 1 crystallizes in monoclinic system, space group Pnma with a = 8.9731(5), b = 22.0477(12), c = 10.0217(5) ?, V = 1982.66(18) ?3, Z = 8, C10 H6 ZnN3 O2, Mr = 265.55, Dc = 1.779 g/cm3, μ = 2.462 mm-1, F(000) = 1064, the final R = 0.0225 and wR = 0.0652 with I > 2σ(I). This complex is a 3 D framework with the(42,62,82)(4,62,83) topology. Furthermore, the thermal stability of complex 1 is observed to be dependent on the polymeric structure nature. Strong solid-state luminescence emissions suggest that complex 1 is a good candidate for light emission materials.

关键词： crystal structure thermal stability zinc(Ⅱ) complex luminescence properties

Two Preparation Methods-dominated Cd^(Ⅱ)-Based Coordination Polymers with Mixed Adenine Nucleobase and 5-Nitroisophathalate Ligands: Synthesis, Structure and Fluorescence

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Chinese Journal of Structural chemistry 2019年第4期38卷 613-620页

作者： LIU Zheng-Yu FU Min WANG Xiu-Guang WANG Li-Li YANG En-Cui ZHAO Xiao-Jun College of chemistry Key Laboratory of Inorganic-Organic Hybrid Functional Material ChemistryMinistry of Education Tianjin Key Laboratory of Structure and Performance for Functional Molecules Tianjin Normal University

Two new CdⅡ-based coordination polymers(CPs) with mixed adenine(Hade) nucleobase and 5-nitroisophathalate(nip) ligands, {[Cd(Hade)_(0.5)(H_2O)_2(nip)]·H_2O}n 1 and {[Cd(Hade)(H_2O)_(1.25)(CH_3OH)0.75(nip)]·0.75 CH_3OH·0.5H_2 O}_n 2, were successfully obtained by varying the preparation methods and structurally characterized. Crystal data for 1: monoclinic, C2/c space group with a = 10.5546(6), b = 17.3496(6), c = 16.1198(9) ?, β = 104.2800(10)o, V = 2860.6(2) ?3, Dc = 2.058 g/cm^3, Mr = 443.13, Z = 8, F(000) = 1752, μ = 1.585 mm^(–1), the final R = 0.0394 and wR = 0.1109 for 2285 observed reflections with I > 2σ(I). For 2: triclinic, P1 space group with a = 10.2032(7), b = 10.5098(8), c = 11.0223(8) ?, a = 65.7050(10)o, β = 74.5750(10)o, g = 61.5280(10)o, V = 943.38(12) ?~3, Dc = 1.888 g/cm3, Mr = 536.24, Z = 2, F(000) = 537, μ = 1.225 mm^(–1), the final R = 0.0225 and wR = 0.0702 for 3143 observed reflections with I > 2σ(I). 1 presents a crisscrossed layer with mutually orthogonal {Cd(nip)} chains aggregated by neutral m-N(7),N(9)-Hade connector. By contrast, 2 displays a linear chain with CdⅡ ions extended by bis-bidentate chelating-nip2–connectors, which are further assembled into a broad ribbon by N-H···N hydrogen-bonding interactions. Additionally, the two solid-state samples with comparable thermal stability exhibit favorable luminescent emissions at room temperature, suggesting their potential applications as fluorescence materials.

关键词： adenine nucleobase coordination polymer crystal structure fluorescence

Synthesis and Crystal Structure of 5,5'-Bis(4-hydroxylphenyl)diazo-dipyrromethane

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Chinese Journal of Structural chemistry 2013年第7期32卷 1093-1099页

作者：史红梅尹振明 Tianjin key laboratory of Structure and Performance for functional Molecules key laboratory of inorganic-organic Hybrid functional material chemistry Ministry of Education College of chemistry Tianjin Normal University

A new 5,5＇-bisdiazo dipyrromethane, compound 2, has been synthesized and cha- racterized. The crystal of 2 is of monoclinic, space group P21/c with a = 16.3185（10）, b = 20.8225（13）, c = 18.5985（11））k, β = 114.5280（10）°, V = 5749.3（6））A^3, Z = 8, C25H26N602, Mr= 442.52, Dc= 1.022 g/cm, F（000） = 1872,/x（MoKa） = 0.068 mmI. The final R = 0.0469 and wR = 0.1143 for 10119 observed reflections with I 〉 2tr（/）, and R = 0.0677 and wR = 0.1231 for all reflections. The title compound prefers to form interlocked type dimer through quadruple N-H...N hydrogen bonds. The dimers self-assemble into a porous 3-D structure through O-H...O and C-H...N hydrogen bonds.

关键词： 5,5'-bisdiazo-dipyrromethane hydrogen-bonded self-assembly porous

Synthesis,Structure and Magnetism of Two Cu(Ⅱ) 4,5-Dichlorophthalate Complexes

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Chinese Journal of Structural chemistry 2015年第12期34卷 1862-1868页

作者：崔红旺夏燕飞项炘欣秦绍恒杨恩翠 College of chemistry Key Laboratory of Inorganic-organic Hybrid Functional Material Chemistry Ministry of Education Tianjin Key Laboratory of Structure and Performance for Functional Molecules Tianjin Normal University

Two 4,5-dichlorophthalate-based metal complexes, {[Cu（bipy）（dcpa）].H2O}n, （1） and {[Cu2Coipy）2（Hdcpa）3]·H2O·***} （2, H2dcpa = 4,5-dichlorophthalic acid and bipy = 2,2＇-bipyridine）, were synthesized and characterized structurally and magnetically. Complex 1 is of orthorhombic system, space group Fdd2 with a = 20.5821（8）, b = 20.9013（12）, c = 17.0270（7） A, V= 7324.9（6） A3, Dc = 1.707 g/cm3, Mr = 470.74, Z = 16, F（000） = 3792, p = 1.519 mm^-1, the final R = 0.0223 and wR = 0.0549 for 9239 observed reflections with I〉 2σ（I）. Complex 2 crystallizes in triclinic, space group P1 with a = 14.1439（12）, b = 14.2981（12）, c = 15.1054（14） A, a = 72.121（2）, β = 77.703（2）,γ = 81.829（2）°, V= 2830.9（4） A3, Dc = 1.689 g/cm3, M,. = 1439.55, Z = 2, F（000） = 1452,μ = 1.207 mm^-1, the final R = 0.0536 and wR = 0.0981 for 16422 observed reflections with 1 〉 2σ（I）. Complex 1 exhibits a diamond-like framework with centrosymmetric binuclear subunits extended by pairs of doubly deprotonated dcpa2- linkers. By contrast, 2 is an asymmetric binuclear entity bridged by carboxylate group of mono deprotonated Hdcpa- ligands. Weak anti- and ferromagnetic interactions are respectively mediated in the carboxylate aggregated binuclear subunits of 1 and 2.

关键词： 4,5-dichlorophthalate Cu(II) complex crystal structure magnetism

Recent advances in BiOBr-based photocatalysts for environmental remediation

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Chinese Chemical Letters 2021年第11期32卷 3265-3276页

作者： Lingyou Meng Yang Qu Liqiang Jing key laboratory of functional inorganic materials chemistry School of Chemistry and Material SciencesHeilongjiang UniversityHarbin 150080China

The efficient utilization of solar energy through photocatalysis is ideal for solving environmental issues and the development sustainable ***-based semiconductors possess unique narrowed bandgaps and layered structures,thereby widely studied as photocatalysts for environmental ***,a little has been focused on the comprehensive reviewing of BiOBr despite its extensive and promising *** this review,the state-of-the-art developments of BiOBr-based photocatalysts for environmental remediation are *** focus is paid to the synthetic strategies for the control of the resulting morphologies,as well as efficient modification strategies for improving the photocatalytic *** include boosting the bulk phase by charge separation,enhancing the spatial charge separation,and engineering the surface *** environmental uses of BiOBr-based photocatalysts are also reviewed in terms of purification of pollutants and CO_(2) ***,future challenges and opportunities of BiOBr-based materials in photocatalysis are ***,this review provides a good basis for future exploration of high-efficiency solar-driven photocatalysts for environmental sustainability.

关键词： BiOBr Visible-light photocatalysis Electron modulation Charge separation Environmental remediation

Synthesis, Structure and Photocatalytic Activity of Two 4-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)benzoate-Based Chain Complexes

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Chinese Journal of Structural chemistry 2018年第5期37卷 803-810页

作者：王志宏郝瑞祝爽赵小军 College of chemistry Key Laboratory of Inorganic-organic Hybrid Functional Material Chemistry Ministry of Education Tianjin Key Laboratory of Structure and Performance for Functional Molecules Tianjin Normal University

Two new one-dimensional chains extended by alternate benzenedicarboxylate（BDC） and 4-（2,6-di（pyrazin-2-yl）pyridin-4-yl）benzoate（L-） connectors, {[Cu（L）（BDC）（0.5）]·3.5 H2 O}n （1） and {[Zn（L）（BDC）（0.5）] ·H2 O}n （2）, were solvothermally synthesized. Complex 1 is in triclinic system, space group P1 with a = 9.6456（14）, b = 11.1160（16）, c = 12.0414（18） A, α = 106.266（3）, β = 92.277（3）, γ =108.104（3）°, V = 1166.6（3） A3, Dc = 1.603 g·cm（-3）, Mr = 563.00, Z = 2, F（000） = 578, μ = 0.996 mm（-1）, the final R = 0.0575 and wR = 0.1386 for 3704 observed reflections with I ＆gt; 2σ（I）. Complex 2 crystallizes in monoclinic, space group C2/c with a = 28.607（5）, b = 8.9767（16）, c = 19.705（4）？, β = 125.396（3）°, V = 4125.0（13）？3, Dc = 1.674 g·cm（-3）, Mr = 519.79, Z = 8, F（000） = 2120, μ = 1.242 mm（-1）, the final R = 0.0487 and w R = 0.0907 for 2944 observed reflections with I ＆gt; 2σ（I）. Resulting from the narrower band gap and broader response to visible light, the CuII-chain exhibits better photocatalytic performance towards the degradation of rhodamine B and methylene blue than those of ZnII-chain.

关键词： 4-(2,6-di(pyrazin-2-yl)pyridin-4-yl)benzoate photocatalytic activity crystal structure coordination polymer

Nanoscale and hollow inorganic sulfide@porous organic network doped intelligent hydrogels for accelerating diabetes wound therapeutics

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Science China chemistry 2025年

作者： Yanhong Li Qiang Zhang Quanbo Wang Junping Wang Xiaomei Zhang Caixia Yin School of chemistry and Chemical Engineering Shandong University key laboratory of Chemical Biology and Molecular Engineering of Ministry of Education Shanxi University

Diabetic wound healing remains a major challenge due to the excess hyperglycemia microenvironment,massively bacterial infections,macrophage dysfunction,and persistent *** comprehensively solve these problems,novel multifunctional materials are highly ***,a versatile and intelligent hydrogel (Cu2S@FePPOPTPM@GOx@Gel) is ***2S@FePPOPTPM@GOx with hollow morphology and controllable size was rationally designed and fabricated by using Cu2S nanocubes as a template,followed by in situ growth of FePPOPTPMand loading glucose oxidase （GOx）,*** infection occurs,the Schiff base bonds in Cu2S@FePPOPTPM@GOx@Gel can controllably release Cu2S@FePPOPTPM@GOx based on its excellent dynamic pH-responsiveness,thereby synergically reducing blood glucose levels and killing bacteria achieved relying on the excellent catalytic activity of GOx towards glucose and its promoted peroxidelike activity of *** experiments on diabetic wound model in vivo demonstrated that Cu2S@FePPOPTPM@GOx@Gel promoted wound healing and skin regeneration,which was attributed to its antibacterial properties,alleviating inflammation,stimulating vascular regeneration,and encouraging M2 polarization of *** work provides a novel strategy for the construction of a microenvironment-responsive and antibiotics-free drug delivery platform to treat diabetic wounds,as well as broad prospects of nanomaterials in the clinical treatment of chronic wounds.

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Advancements and Challenges in Organic–inorganic Composite Solid Electrolytes for All‑Solid‑State Lithium Batteries

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Nano-Micro Letters 2025年第1期17卷 46-97页

作者： Xueyan Zhang Shichao Cheng Chuankai Fu Geping Yin Liguang Wang Yongmin Wu Hua Huo State key laboratory of Space Power‑Sources School of Chemistry and Chemical EngineeringHarbin Institute of TechnologyHarbin 150001People’s Republic of China College of Chemical and Biological Engineering Zhejiang UniversityHangzhou 310058People’s Republic of China State key laboratory of Space Power-Sources 2965 Dongchuan RoadMinhang DistrictShanghai 200240People’s Republic of China

To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming *** the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale ***,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their *** review provides a comprehensive overview of recent research advancements in ***,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically *** lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic ***,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of ***,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.

关键词： Composite solid electrolytes inorganic filler Interfacial stability Li-ion conduction mechanism Characterization techniques