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Solvent-induced diversity of luminescent metal–organic frameworks based on different secondary building units

机译:溶剂诱导的基于不同二级建筑单元的发光金属-有机骨架的多样性

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By using a symmetrical V-shaped rigid 5′-carboxyl-(1,1′-3′,1′′-terphenyl)-4,4′′-dicarboxylic acid (H3L), three Cd(II)-based metal–organic frameworks (MOFs), [Cd3(L)2(H2O)4]·DMF (1), [Cd2(L)(SO4)2]·3(Me)2NH2 (2) and [Cd(HL)(H2O)]·0.5H2O (3), have been synthesized under solvothermal conditions. Due to the reactions in different solvent systems, L3?/HL2? in 1–3 show different coordination modes with Cd(II) ions to form various secondary building units (SBUs) in the final structures. The desolvated structure of 1 (1a) contains two shapes of 1D channels with suitable pore sizes. 2 is a 3D dense packing pattern with a three nodal (5,6,7)-connected new topological net, and 3 is a 2D layered (4,4)-connected sql network connected with partly deprotonated HL2? ligands. As a result, 1a possesses not only high CO2 loading but also excellent CO2/CH4 selectivity. In addition, all complexes display solid-state luminescence stemming from ligand-to-metal charge transfer.
机译:通过使用对称的V形刚性5'-羧基-(1,1'-3',1''-三联苯)-4,4''-二羧酸(H 3 L),三个基于Cd( II )的金属有机框架(MOF),[Cd 3 (L)< small> 2 (H 2 O) 4 ]· DMF(1),[Cd 2 (L)(SO 4 2 ]·3(Me) 2 NH 2 (2)和[ Cd(HL)(H 2 O)]·0.5H 2 O(3),已经合成在溶剂热条件下。由于溶剂系统中的反应不同,1-3中的L 3? / HL 2? 显示不同与Cd( II )离子的配位模式在最终结构中形成各种二级建筑单元(SBU)。 1(1a)的去溶剂化结构包含具有合适孔径的两种形状的1D通道。 2是带有3个节点(5,6,7)连接的新拓扑网络的3D密集堆积模式,而3是2D分层(4,4)连接的sql网络和部分去质子化的HL 2个? 配体。结果,1a不仅具有较高的CO 2 负载,而且具有出色的CO 2 / CH 4 选择性。此外,所有配合物均显示出源自配体至金属的电荷转移的固态发光。

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