Yang Sihai, Lin Xiang, Dailly Anne, Blake Alexander J, Hubberstey Peter, Champness Neil R, Schröder Martin
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Chemistry. 2009;15(19):4829-35. doi: 10.1002/chem.200802292.
Solvothermal reaction of the ligands H(4)L(110) ((2,7-phenanthrenediyl)diisophthalic acid) and H(4)L(111) ([2,7-(9,10-dihydrophenanthrenediyl)]diisophthalic acid) with Cu(NO(3))(2) x 2.5 H(2)O in a slightly acidified mixture of DMF/1,4-dioxane/H(2)O afforded the solvated framework compounds Cu(2)(L(110))(H(2)O)(2)(7.5)(H(2)O)(5) (NOTT-110) and Cu(2)(L(111))(H(2)O)(2)(7.5)(H(2)O)(5) (NOTT-111), respectively. Crystal structure determinations confirmed that NOTT-110 and NOTT-111 have the same NbO framework structure, differing only at the 9 and 10 positions of the phenanthrene group. The BET surface areas for desolvated NOTT-110 and NOTT-111 were estimated to be 2960 and 2930 m(2) g(-1), respectively. Compared with their phenyl analogues, introduction of phenanthrene groups to these porous Cu(II)-carboxylate framework materials leads to an enhancement of H(2) adsorption. Thus, the H(2) isotherms for desolvated NOTT-110 and NOTT-111 confirm 2.64 and 2.56 wt % total H(2) uptake, respectively, at 1 bar and 78 K. NOTT-110 shows a high total H(2) storage capacity of 7.62 wt % at 55 bar and 77 K (8.5 wt % at saturation) with a total volumetric capacity of 46.8 g L(-1) at 55 bar and 77 K.
配体H(4)L(110)（(2,7-菲二基)二间苯二甲酸）和H(4)L(111)（[2,7-(9,10-二氢菲二基)]二间苯二甲酸）与Cu(NO(3))(2)·2.5H(2)O在微酸化的N,N-二甲基甲酰胺/1,4-二氧六环/水混合溶剂中进行溶剂热反应，分别得到溶剂化骨架化合物Cu(2)(L(110))(H(2)O)(2)(7.5)(H(2)O)(5)（NOTT-110）和Cu(2)(L(111))(H(2)O)(2)(7.5)(H(2)O)(5)（NOTT-111）。晶体结构测定证实，NOTT-110和NOTT-111具有相同的NbO骨架结构，仅在菲基的9位和10位有所不同。脱溶剂后的NOTT-110和NOTT-111的BET表面积估计分别为2960和2930 m(2) g(-1)。与它们的苯基类似物相比，将菲基引入这些多孔Cu(II)-羧酸盐骨架材料中会导致H(2)吸附增强。因此，脱溶剂后的NOTT-110和NOTT-111的H(2)等温线证实，在1 bar和78 K下，H(2)的总吸附量分别为2.64 wt%和2.56 wt%。NOTT-110在55 bar和77 K下显示出7.62 wt%的高总H(2)存储容量（饱和时为8.5 wt%），在55 bar和77 K下的总体积容量为46.8 g L(-1)。
