The reaction of propargylic amines and CO 2 can provideh igh-value-added chemical products.H owever,m ost of catalysts in such reactions employn oble metals to obtain high yield, and it is important to seek eco-friendly noble-metalfree MOFs catalysts.H ere,agiant and lantern-like [Zn 116 ] nanocage in zinc-tetrazole 3D framework [Zn 22 (Trz) 8 (OH) 12 -(H 2 O) 9 ·8 H 2 O] n Trz = (C 4 N 12 O) 4À (1)w as obtained and structurally characterized.I tc onsists of six [Zn 14 O 21 ]c lusters and eight [Zn 4 O 4 ]c lusters.T oo ur knowledge,t his is the highestnuclearity nanocages constructed by Zn-clusters as building blocks to date.Importantly,catalytic investigations reveal that 1 can efficiently catalyze the cycloaddition of propargylic amines with CO 2 ,e xclusively affording various 2-oxazolidinones under mild conditions.I ti st he first eco-friendly noblemetal-free MOFs catalyst for the cyclization of propargylic amines with CO 2 .DFT calculations uncover that Zn II ions can efficiently activate both C Cbonds of propargylic amines and CO 2 by coordination interaction. NMR and FTIR spectroscopy further prove that Zn-clusters play an important role in activating CCbonds of propargylic amines.Furthermore,the electronic properties of related reactants,i ntermediates and products can help to understand the basic reaction mechanism and crucial role of catalyst 1. Scheme 2. a) Reaction pathway for cycloaddition of CO 2 with propargylic amines obtained utilizing climbingimage nudged elastic band method;b)The reaction energies (E react )o fsubstrate molecules and CO 2 and the corresponding yield of oxazolidinones. Angewandte Chemie Forschungsartikel 8669

A room-temperature MOF-based porous liquid was prepared and showed an outstanding CO2 uptake capacity.

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