摘要
In this paper,we designed and synthesized three novel free-base imidazolyl porphyrins via the Macdonald[2+2]method,and their reactions with different metal ions afforded three new metalloporphyrin frameworks(MPFs)[Co(tBu-Ph)_(2)(Im-Ph)_(2)Por]·2DMF(1),[Co(F_(3)-Ph)_(2)(Im-Ph)_(2)Por]·1.5DMF(2),and[Fe(Me2N,F4-Ph)_(2)(Im-Ph)_(2)Por]·3DMF(3),which display rich structural diversity.Complexes 1 and 2 are isostructural two-dimensional(2D)grid layers,which feature the rare rotaxane-like bilayer and an offset-stacking ABCD fashion of layers,as well as the significantly saddled porphyrin macrocycles.Differently,complex 3 forms a 4-connected lvt 3D framework with the slightly ruffled porphyrin macrocycles,which contains not only interesting helical channels but also uncommon tetrahedral cages.Gas adsorption studies of three complexes reveal the moderate CO_(2) adsorption capacity.Meanwhile,all three complexes exhibit preferable catalytic activity for ethylbenzene oxidation.
基金
the research grant provided by the National Natural Science Foundation of China(21271148,21671158 and 21471124)
the Natural Science Foundation of Shaanxi province(2013KJXX-26 and 2014JQ2049).
