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•A new 3D porous NbO-type MOF with inserted acylamide units was synthesized.•This complex shows large CO 2 -uptake capacity and high selectivity toward CO 2 /N 2 .•This complex exhibits catalytic activity in Knoevenagel condensation reaction.•This work will enrich the chemistry of functional MOFs via inserting polar units.•This work will facilitate research of MOFs with high...
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