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A 2D to 3D solvent mediated transformation of a photoreactive lanthanum MOF: A case of three parallel photo-cycloaddition reactions

Abstract

The 3D Lanthanum-dicarboxylate MOF [La2(hex)3(H2O)4]3H2O, (1), (hex=trans,trans-muconic acid) has been obtained at 50°C, in a silica gel column, either via in situ transformation of the 2D MOF [La2(hex)3(H2O)6]9H2O, (2), published previously, or directly. The structure is made up of metal-ligand layers pillared by a ligand dianion. Comparison of the crystal structures of the two MOFs allowed us to propose a possible mechanism of the 2D to 3D transformation. The presence of many short olefinic contacts allowed formation of three photoproducts at different yields, the major one being the rtct isomer for the 3D MOF and the rttc one for the 2D MOF. In both cases the three photoreactions proceed with the parallel reaction scheme. Comparison of the crystal structures of 1 and 2 allowed to explain the photoreactivity differences observed.

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Publication details

The article was received on 21 Nov 2018, accepted on 09 Jan 2019 and first published on 09 Jan 2019


Article type: Paper
DOI: 10.1039/C8CE01983E
Citation: CrystEngComm, 2019, Accepted Manuscript
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    A 2D to 3D solvent mediated transformation of a photoreactive lanthanum MOF: A case of three parallel photo-cycloaddition reactions

    S. Skoulika, A. Michaelides and M. G. Siskos, CrystEngComm, 2019, Accepted Manuscript , DOI: 10.1039/C8CE01983E

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