Gould Jamie A, Athwal Harprit Singh, Blake Alexander J, Lewis William, Hubberstey Peter, Champness Neil R, Schröder Martin
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK.
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK
Philos Trans A Math Phys Eng Sci. 2017 Jan 13;375(2084). doi: 10.1098/rsta.2016.0334.
A family of Cu(II)-based metal-organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, HL (4'-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), HL (4''-(pyridin-4-yl)-1,1':4',1''-terphenyl-3,5-dicarboxylic acid) and HL (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu(OCR)N] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with HL, which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L)] and the isomers of [Cu(L)], [Cu(L)] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L)] were investigated with N, CO and H, and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO [Cu(L)] displays high H adsorption, with the density in the pores approaching that of liquid HThis article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.
利用三种吡啶基间苯二甲酸配体，即HL（4'-(吡啶-4-基)联苯-3,5-二羧酸）、HL（4''-(吡啶-4-基)-1,1':4',1''-三联苯-3,5-二羧酸）和HL（5-[4-(吡啶-4-基)萘-1-基]苯-1,3-二羧酸），合成了一系列基于Cu(II)的金属有机框架材料（MOF）。尽管在每种情况下，吡啶基间苯二甲酸配体都采用相同的伪八面体[Cu(OCR)N]桨轮配位模式，但所得框架结构多样，特别是在Cu(II)与HL形成的配合物中，这导致了三种不同的超分子异构体，每种异构体都源自 Kagomé 网和方形网。与[Cu(L)]及其异构体相比，[Cu(L)]具有永久孔隙率。因此，研究了[Cu(L)]对N₂、CO₂和H₂的气体吸附性能，该材料表现出与领先的用于CO₂的MOF吸附剂相当的等量吸附热。[Cu(L)]对H₂显示出高吸附性，孔内密度接近液态H₂的密度。本文是主题为“配位聚合物和金属有机框架：设计材料”的特刊的一部分。
