Lü Jian, Perez-Krap Cristina, Trousselet Fabien, Yan Yong, Alsmail Nada H, Karadeniz Bahar, Jacques Nicholas M, Lewis William, Blake Alexander J, Coudert François-Xavier, Cao Rong, Schröder Martin
Fujian Provincial Key Laboratory of Soil Environmental Health and Regulation, College of Resources and Environment, Fujian Agriculture and Forestry University, Fuzhou 350002, P. R. China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.
Cryst Growth Des. 2018 Apr 4;18(4):2555-2562. doi: 10.1021/acs.cgd.8b00153. Epub 2018 Feb 16.
Controlled assembly of two-dimensional (2D) supramolecular organic frameworks (SOFs) has been demonstrated through a binary strategy in which 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)naphthalene (), generated by oxidative dehydrogenation of 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)naphthalene (), is coupled in a 1:1 ratio with terphenyl-3,3',4,4'-tetracarboxylic acid (; to form ), 5,5'-(anthracene-9,10-diyl)diisophthalic acid (; to form ), or 5,5'-bis-(azanediyl)-oxalyl-diisophthalic acid (; to form ). Complementary O-H···N hydrogen bonds assemble 2D 6- (honeycomb) subunits that pack as layers in to give a three-dimensional (3D) supramolecular network with parallel channels hosting guest DMF (DMF = ,'-dimethylformamide) molecules. and feature supramolecular networks of 2D → 3D inclined polycatenation of similar layers as those in . Although suffers framework collapse upon guest removal, the polycatenated frameworks of and exhibit excellent chemical and thermal stability, solvent/moisture durability, and permanent porosity. Moreover, their corresponding desolvated (activated) samples and display enhanced adsorption and selectivity for CO over N and CH. The structures of these activated compounds are well described by quantum chemistry calculations, which have allowed us to determine their mechanical properties, as well as identify their soft deformation modes and a large number of low-energy vibration modes. These results not only demonstrate an effective synthetic platform for porous organic molecular materials stabilized solely by primary hydrogen bonds but also suggest a viable means to build robust SOF materials with enhanced gas uptake capacity and selectivity.
通过二元策略已证明了二维（2D）超分子有机框架（SOF）的可控组装，其中由1,4 - 双 -（4 -（3,5 - 二氰基 - 2,6 - 二吡啶基）二氢吡啶基）萘（）氧化脱氢生成的1,4 - 双 -（4 -（3,5 - 二氰基 - 2,6 - 二吡啶基）吡啶基）萘（）与三联苯 - 3,3',4,4'-四羧酸（；形成）、5,5' -（蒽 - 9,10 - 二基）二间苯二甲酸（；形成）或5,5' - 双 -（氮杂二亚基） - 草酰 - 二间苯二甲酸（；形成）以1:1的比例偶联。互补的O - H···N氢键组装二维6 -（蜂窝状）亚基，这些亚基在中堆积成层，形成具有容纳客体N,N - 二甲基甲酰胺（DMF = ，'-二甲基甲酰胺）分子的平行通道的三维（3D）超分子网络。和具有与中类似层的二维→三维倾斜多链化的超分子网络。尽管在去除客体后会发生框架坍塌，但和的多链化框架表现出优异的化学和热稳定性、溶剂/水分耐久性以及永久孔隙率。此外，它们相应的脱溶剂（活化）样品和对CO的吸附和选择性相对于N和CH有所增强。这些活化化合物的结构通过量子化学计算得到了很好的描述，这使我们能够确定它们的力学性能，以及识别它们的软变形模式和大量低能量振动模式。这些结果不仅证明了一个仅由初级氢键稳定的多孔有机分子材料的有效合成平台，而且还提出了一种构建具有增强气体吸收能力和选择性的坚固SOF材料的可行方法。
