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Porous organic cages as a novel platform for second harmonic generation

Science China Chemistry 2024年第11期67卷 3669-3674页

作者： Feng Shui Yunqin Zhang Mao Yi Xiongli Liu Lin Li Shuo Zhang Yongshen Zheng Yongtao Yao Qiao Zhao Baiyan Li xianhe bu School of Materials Science and Engineering National Institute for Advanced Materials TKL of Metal and Molecule-Based Material Chemistry Nankai University National Key Laboratory of Science and Technology on Advanced Composites in Special Environments Harbin Institute of Technology

Second harmonic generation(SHG) is one of the most extensively applied nonlinear optical phenomena. Compared to traditional inorganic SHG materials, organic SHG materials, including non-centrosymmetric small molecular crystals and organic polymers, have been extensively explored for SHG optics due to their advantageous properties, including high light-induced damage threshold, ultrafast response speed, high polarization ratio, wide transparency range, and elevated dielectric constant. However,in organic SHG materials, most small molecular crystals often show poor thermal stability(bution, we developed herein porous organic cages(POCs) as a novel platform for SHG optics. Thanks to its inherent macromolecular composition and zero-dimensional discrete structures, POCs can not only solve the instability problem of small molecule crystals but also overcome the drawbacks in growing large-size crystals for organic polymer. The obtained two POCs with chiral asymmetric centers(CPOC-R-5 and CPOCS-7) display advantageous features for SHG optics including well SHG performance, large-size crystal(5 mm×3 mm×1 mm),high thermal stability(≥250 °C), wide transparency window(750–2,000 nm) and high polarization ratio(up to 94.5%). This work thus develops POCs as a new platform toward the construction of organic NLO materials with the potential application in sorts of SHG optics.

关键词： porous organic cages second harmonic generation novel SHG platform high thermal stability large-size single crystal

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Highlights of recent advances in functional coordination polymers made in China

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Chinese Science bulletin 2011年第21期56卷 2297-2299页

作者： DU Miao CHEN YongQiang bu xianhe College of Chemistry Tianjin Key Laboratory of Structure and Performance for Functional MoleculeTianjin Normal UniversityTianjin 300387China Department of Chemistry Tianjin Key Laboratory of Metal-and Molecule-Based Material ChemistryNankai UniversityTianjin 300071China

Coordination polymers (or metal-organic frameworks, MOFs), as one of the essences of crystal engineering and coordination chemistry, have attracted considerable atten-tion from chemists,

关键词：配位聚合物中国超分子结构材料科学家金属有机配位化学晶体工程物理学家

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Synthesis, structure and magnetic properties of two new coordination polymers with carboxylate-substituted benzoimidazole ligands

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Science China Chemistry 2009年第9期52卷 1451-1455页

作者： HU BoWen ZHAO JiongPeng YANG Qian ZHANG XiaoFeng bu xianhe Department of Chemistry Nankai UniversityTianjin 300071China

This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands: [Mn(L)·(HCO2)] n (1) and [Co(L)·(HCO2)] n (2) (L = benzoimidazol-1-yl-acetate). Complexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing interesting magnetic properties: spin canted antiferromagnetism for MnII complex 1, but simple antiferromagnetic coupling for CoII complex 2.

关键词： carboxylate-substituted benzoimidazole formate magnetic property synthesis structure

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A cationic metal-organic framework based on {Zn4} cluster for rapid and selective adsorption of dyes

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Chinese Chemical Letters 2018年第6期29卷 857-860页

作者： Weiwei He Na Li Xi Wang Tongliang Hu xianhe bu Department of Chemistry Nankai University School of Materials Science and Engineering National Institute for Advanced Materials Nankai University Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education)and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Nankai University

Until now, to remove the harmful organic dyes from effluents is an outstanding challenge. The design and synthesis of new porous materials capable of selectively adsorbing dyes are critical to the environment and human health. Here, a unique cluster-based cationic metal-organic framework, named{[Zn8（BTA）6（L）5Cl2]·（NO3）3}·5 DMF（NUM-4） was synthesized, which displays one-dimensional（1 D）open channels along a axis in its 3 D supramolecular stacking structure. Benefiting from the nature of cationic framework and high surface area/pore volume, NUM-4 shows rapid and selective adsorption of anionic dyes（MO, AO, CR and MB） based on the charge-exclusive effect. Besides, the adsorbed dyes can be easily released in NH4Cl saturated solution of ethanol.

关键词： Metal-organic framework Supermolecule Anionic dyes Adsorption and separation Charge-exclusive effect

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Syntheses, structures and magnetic properties of three Co(Ⅱ)coordination architectures based on a flexible multidentate carboxylate ligand and different N-donor ligands

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Science China Chemistry 2013年第12期56卷 1693-1700页

作者： TIAN Dan LIU SuiJun ZHANG DaShuai CHANG Ze HU TongLiang bu xianhe Department of Chemistry and TKL of Metal- and Molecule-Based Material Chemistry Nankai University

Three new cobalt complexes, {[Co5（tci）2（bimb）3（μ3-O）2（H2O）2]·3DMF·4H2O}n（1）, {[Co3（tci）2（bib）]·2DMF·2H2O}n （2） and {[Co（Htci）（bpea）0.5]-H2O}n （3）（H3tci = tris（2-carboxyethyl）isocyanurate, bimb = 4,4＇-bis（imidazol-l-yl）biphenyl, bib = 1,4-bis（imidazol-l-yl）benzene, bpea = 1,2-bis（4-pyridyl）ethane, DMF = N,N＇-dimethylformamide）, have been successfully synthesized through the assembly of Co（If） ions, H3tci and different N-donor ligands, respectively. All complexes were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric （TG） analyses and X-ray powder diffraction （XRPD）. Complex 1 exhibits a 3D three-fold parallel interpenetrated 3D · 3D structure with （65.8） CdSO4 topology. Complex 2 is built from [Co3（μ/2-Ocarboxyl）2（CO2）4] clusters and linear bib ligands, displaying a two-fold par- allel interpenetrated （3,8）-connected （4^3）2（4^6.6^18·8^4） topology, while complex 3 is a 3D pillar-layered structure involving an in- finite -Co-（μ2-Ocarboxyl）（CO2）-Co-chain. The diverse structures of the three complexes indicate that the skeletons of different N-donor ligands play an important role in the assembly of such different frameworks. In addition, magnetic investigation indi- cates that besides spin-orbit coupling of Co（II） ions, there exist antiferromagnetic exchange interactions in Co5 and Co3 clus- ters of 1 and 2, respectively.

关键词： Coordination polymers cobalt clusters topology magnetic properties

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Syntheses, structures and magnetic properties of Fe6 and Fe12 ferric wheels

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Science China Chemistry 2015年第12期58卷 1853-1857页

作者： Guojian Ren Yanqing Liu Zhenxin Zhao Suijun Liu Songde Han Jian Xu xianhe bu Department of Chemistry Tianjin Key Lab of Metal- and Molecule-Based Material Chemistry and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Nankai University

Starting from the same Fe3O(RCO2)6 complex and using a similar synthesis strategy, the Fe6 and Fe12 wheels were obtained by utilizing two designed ligands, 2-amino-2-methyl-1,3-propanediol(L1) and 1,3-propanediol(L2), respectively. A biological buffer reagent, Bis-Tris(2-[bis-(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol) was first introduced in the synthesis of the Fe12 wheel, playing a vital role in adjusting the acidity of reaction environment. Magnetic studies on both Fe6 and Fe12 wheels revealed strong antiferromagnetic coupling between the spins on FeIII ions.

关键词： ferric wheel syntheses Bis-Tris magnetic properties

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Structure and magnetism of carboxylate/EO-azido-mixed-ligands bridged Cu~Ⅱ systems

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Chinese Science bulletin 2009年第23期54卷 4303-4308页

作者： ZHAO JiongPeng HU BoWen YANG Qian LIU FuChen HU TongLiang bu xianhe Department of Chemistry Nankai University Tianjin 300071 China

Using two structurally related benzoates bearing different H-bond acceptors as co-ligands, three new azido-CuⅡ compounds, [Cu(L1)(N3)(H2O)]n (1), [Cu(L1)(N3)(MeOH)]n (2), and [CuL2HL2(N3)3(H2O)]n (3) (HL1 = 4-nitrobenzoic acid; HL2 = 2-phenyl-4-quinolinecarboxylic acid), have been synthesized and structurally characterized. 1 is a carboxylate/EO-azido bridged copper chain, forming 3D structure by H-bonds, and 2 has a similar chain structure as 1 but forming a 2D structure by H-bonds, while 3 is a 3D supramolecular network with ternary center H-bonds. Magnetic study indicates that domain ferromagnetic coupling interactions were found to exist in complexes 1 and 3.

关键词：叠氮化合物结构表征混合配体主任行政羧酸硝基苯甲酸铁磁性耦合

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A water-stable lanthanide-coordination polymer with free Lewis site for fluorescent sensing of Fe^(3+)

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Chinese Chemical Letters 2019年第1期30卷 75-78页

作者： Wenhe Wang Qiang Gao Xiaoyu Li Jianhong Wang Chaopeng Wang Yinghui Zhang xianhe bu Department of Chemistry Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Nankai University School of Materials Science and Engineering TKL of Metal- and Molecule-Based Material Chemistry Nankai University

A new fluorescent coordination polymer(NKU-115) was constructed under solvothermal condition based on Tb^(3+)ion and H_2L(5-(4 H-1,2,4-triazol-4-yl) benzene-1,3-dicarboxylic acid) ligand, featuring high solvent and water stability. Luminescent investigations revealed that NKU-115 shows fluorescence quenching response toward Fe^(3+)in aqueous solution and the mechanism of quenching was analyzed.

关键词： Lanthanide-based coordination polymers Fluorescent sensing Aqueous solution Lewis site Iron ion

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Three new Cu(Ⅱ)-Ln(Ⅲ) heterometallic coordination polymers constructed from quinolinic acid and nicotinic acid: Synthesis, structures, and magnetic properties

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Science China Chemistry 2012年第6期55卷 1064-1072页

作者： LIU SuiJun SONG WeiChao XUE Li HAN SongDe ZENG YongFei WANG LiFu bu xianhe Department of Chemistry Tianjin Key Laboratory of Metal & Molecule-based Material Chemistry Nankai University Tianjin 300071 China

Three new Cu（Ⅱ）-Ln（Ⅲ） heterometallic coordination polymers based on two N-heterocyclic carboxylic ligands, {[LnCu（LI）2（L2）（H2O）2]· mH20},, （Ln = La（1）, Nd（2）, Gd（3）, m = 2 （for 1）, 1 （for 2, 3）, H2L1 = quinolinic acid, HE2 = nico- tinic acid）, have been synthesized and characterized. 1 has a two-dimensional （2D） layer structure with a Schlifli symbol of （44.62）, while complexes 2 and 3 are isostructural and have three-dimensional （3D） structures with a Schlafli symbol of （3.4.5）2（32.***.52.6]4.***.83.9）（32.63.7） of 3-nodal net. Magnetic investigations suggest that antiferromagnetic coupling exists be- tween NdIn and Cun in 2, while weak ferromagnetic coupling between GdⅢ and CuⅡ in 3. The difference of magnetic properties between 2 and 3 has been discussed.

关键词： Cu(Ⅱ)-Ln(Ⅲ) coordination polymers metal oxides magnetic properties

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Novel coordination polymers with 1,4-di(benzimidazole-1-yl)benzene modulated by an anion:Syntheses,structures and properties

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Science China Chemistry 2010年第10期53卷 2170-2176页

作者： LI Lei, HU TongLiang, ZENG YongFei, bu xianhe TKL of Metal-and Molecule-Based Material Chemistry, Department of Chemistry, Nankai University, Tianjin 300071, China TKL of Metal- and Molecule-Based Material Chemistry Department of Chemistry Nankai University Tianjin China

Three novel coordination polymers, {[Co(L)(SO4)(H2O)](CH3OH)}∞ (1), {[Cd(L)2(SiF6)](H2O)}∞ (2) and [Zn(L)(NO3)2]∞ (3), synthesized from 1,4-di(benzimidazole-1-yl)benzene (L), have been characterized by infrared spectroscopy, elemental analysis and single crystal X-ray diffraction. Compounds 1-3 exhibit different structures. Complex 1 has a 3-D diamond network containing 1-D CoII chains connected by SO24- anions; 2 has a 3-D α-Po framework with 1-D porous channels along the c axis; and 3 has a 1-D zig-zag chain structure with a 2-D supramolecular network based on π-π interactions. The magnetic properties of 1 and the solid state fluorescence spectra of 2 and 3 have also been explored.

关键词： anion effect coordination polymer fluorescence magnetic properties structure

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