Multicopper(II) Pyromellitate Compounds: Self-Assembly Synthesis, Structural Topologies, and Magnetic Features

Karabach YY; Kirillov AM; Haukka M; Sanchiz J; Kopylovich MN; Pombeiro AJL

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Multicopper(II) Pyromellitate Compounds: Self-Assembly Synthesis, Structural Topologies, and Magnetic Features

机译：均苯四酸二铜（II）化合物：自组装合成，结构拓扑和磁性特征

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Self-assembly syntheses based on the reactions, in aqueous solution at room temperature, of copper(II) nitrate, triethanolamine (H(3)tea), pyromellitic acid (H(4)pma), and ammonia or its derivatives (methylamine, ethylamine) give rise to the new Cu(II) 2D [Cu-2(mu(6)-pma)(NH3)(4)](n)center dot 2nH(2)O (1) and 3D [Cu-2(mu-H2O)(2)(mu(4)-pma)(MeNH2)(4)], (2) coordination polymers and the dimer [Cu-2(mu(2)-pma)(H(3)tea)(2)(EtNH2)(2)] (3). A crucial synthetic and structural role is played by ammonia and its derivatives, acting also as pH regulators. 1-3 have been isolated as air-stable crystalline solids and characterized by IR spectroscopy and elemental and single-crystal X-ray diffraction analyses, the latter showing the formation of infinite 2D (1) and 3D (2) metal-organic frameworks or discrete dimeric blocks (3) adopting distinct structural topologies. The structures are further extended through numerous H-bonding interactions to give 3D (1, 2) and ID (3) hydrogen bonded supramolecular assemblies. Magnetic susceptibility measurements reveal weak antiferromagnetic coupling between the copper(II) ions. Compound 1 follows the Bleaney-Bowers dinuclear model, 2 the antiferromagnetic chain model, and 3 the Curie-Weiss law. The weak magnetic coupling is explained in terms of the poor overlap between the magnetic orbitals centered at the copper(II) ions through the bridging ligands.

机译：根据在室温下水溶液中硝酸铜（II），三乙醇胺（H（3）茶），均苯四酸（H（4）pma）和氨或其衍生物（甲胺，乙胺）生成新的Cu（II）2D [Cu-2（mu（6）-pma）（NH3）（4）] [n）中心点2nH（2）O（1）和3D [Cu-2 （mu-H2O）（2）（mu（4）-pma）（MeNH2）（4）]，（2）配位聚合物和二聚体[Cu-2（mu（2）-pma）（H（3）tea ）（2）（EtNH2）（2）]（3）。氨及其衍生物也起着至关重要的合成和结构作用，还起着pH调节剂的作用。 1-3已分离为空气稳定的结晶固体，并通过红外光谱，元素和单晶X射线衍射分析进行了表征，后者显示了无限的2D（1）和3D（2）金属-有机骨架或采用不同结构拓扑的离散二聚体嵌段（3）。通过大量的H键相互作用进一步扩展了结构，从而获得了3D（1、2）和ID（3）氢键超分子组装体。磁化率测量表明铜（II）离子之间的反铁磁耦合很弱。化合物1遵循Bleaney-Bowers双核模型，化合物2遵循反铁磁链模型，化合物3遵循居里-魏斯定律。弱磁耦合的解释是通过桥联配体，以铜（II）离子为中心的磁轨道之间的重叠差。

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《Crystal growth & design》 |2008年第11期|共9页
作者
Karabach YY; Kirillov AM; Haukka M; Sanchiz J; Kopylovich MN; Pombeiro AJL;
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正文语种 eng
中图分类晶体学;
关键词
TRANSITION-METAL-COMPLEXES; COPPER(II) COORDINATION POLYMERS; MILD PEROXIDATIVE OXIDATION; PROTON-TRANSFER REACTION; X-RAY-STRUCTURE; CRYSTAL-STRUCTURE; EXCHANGE INTERACTION; WATER CLUSTERS; 1; 2; 4; 5-BENZENETETRACARBOXYLIC ACID; SUPRAMOLECULAR ARCHITECTURES;

机译：过渡金属络合物;铜（II）配位聚合物;混合过氧化物氧化;质子转移反应;X射线结构;晶体结构;交换相互作用;水团簇;1;2;4;5-苯甲醛建筑结构;

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专利

1. Multicopper(II) Pyromellitate Compounds: Self-Assembly Synthesis, Structural Topologies, and Magnetic Features [J] . Karabach YY, Kirillov AM, Haukka M, Crystal growth & design . 2008,第11期

机译：均苯四酸二铜（II）化合物：自组装合成，结构拓扑和磁性特征
2. Topological Diversity of Supramolecular Networks Constructed from Copper(II) Aminoalcohol Blocks and 2,6-Naphthalenedicarboxylate Linkers: Self-Assembly Synthesis, Structural Features, and Magnetic Properties [J] . Sara S. P. Dias, Vania André, Julia K?ak, Crystal growth & design . 2014,第7期

机译：由铜（II）氨基醇嵌段和2,6-萘二甲酸酯连接基构建的超分子网络的拓扑多样性：自组装合成，结构特征和磁性。
3. Correction:Self-assembly ofmixed-valence Co(II/III) and Ni(II) clusters: azide-bridged 1D single chain coordination polymers comprised of tetranuclear units, tetranuclear Co(II/III) complexes, ferromagnetically coupled azide-bridged tetranuclear, and hexanuclear Ni(II) complexes: synthesis, structural, and magnetic properties (pg 6536, 2010) [J] . Tandon SS, Bunge SD, Rakosi R, Dalton transactions: An international journal of inorganic chemistry . 2010,第47期

机译：校正：混合价Co（II / III）和Ni（II）簇的自组装：叠氮桥联的一维单链配位聚合物，由四核单元，四核Co（II / III）络合物，铁磁耦合的叠氮化物桥联的四核，和六核Ni（II）配合物：合成，结构和磁性能（pg 6536，2010）
4. Insight into the Coordination Chemistry of Plutonium Compounds: Synthesis and Structural Characteristics of Pu(III) Oxalate and Pu(VI) Hydrous Oxides [C] . Wolfgang Runde, Amanda Bean, Brian L. Scott Topical Conference on Plutonium and Actinides . 2003

机译：洞察钚化合物的协调化学物质：PU（III）草酸和PU（VI）含水氧化物的合成和结构特征
5. Photochemistry of group 8 metal complexes of type [M(bpy)2 cyanogen] (M = iron, ruthenium). Photosynthesis of heteroleptic iron(II) compounds and photoionization of ruthenium(II) compounds, or, Photoassisted synthesis of heteroleptic iron(II) compounds and photoionization of ruthenium(II) complexes. [D] . Turner, David Benjamin. 2009

机译：[M（bpy）2氰基]类型的第8组金属配合物的光化学（M =铁，钌）。杂合铁（II）化合物的光合作用和钌（II）化合物的光电离，或者杂合铁（II）化合物的光辅助合成和钌（II）配合物的光电离。
6. Self-Assembly by Tridentate or Bidentate Ligand: Synthesis and Vapor Adsorption Properties of Cu(II) Zn(II) Hg(II) and Cd(II) Complexes Derived from a Bis(pyridylhydrazone) Compound [O] . Hong-Juan Liu, Rui Yi, Dong-Mei Chen, 2021

机译：通过三齿或二齿配体自组装：Cu（II）Zn（II）Hg（II）Hg（II）和Cd（II）复合物的合成和蒸气吸附性能来自双（吡啶基腙）化合物
7. Click chemistry as a route to the synthesis of structurally new and magnetically interesting coordination clusters: a {NiII8} complex with a trapezoidal prismatic topology [O] . Parisa Abbasi, Angeliki A. Athanasopoulou, Eleni C. Mazarakioti, 2019

机译：单击化学作为合成结构新的和磁性有趣的协调簇的途径：具有梯形棱镜拓扑的{NIII8}复合物
8. New Magnetic and Structural Results for Uniformly Spaced, Alternatingly Spaced, and Ladder-Like Copper(II) Linear Chain Compounds [R] . Hatfield, W. E. 1980

机译：均匀间隔，交替间隔和梯形铜（II）线性链化合物的新磁性和结构结果

Multicopper(II) Pyromellitate Compounds: Self-Assembly Synthesis, Structural Topologies, and Magnetic Features

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