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Two (5, 5)-connected isomeric frameworks as highly selective and sensitive photoluminescent probes of nitroaromatics


Herein we report the first two (5, 5)-connected isomeric frameworks, namely (Me2NH2)[Zn2L(H2O)]●3.5DMF (1) and (Me2NH2) [Zn2L(H2O)]●6DMF●4H2O (2) (DMF = dimethylformamide, H5L = 5,5'-(6-(4-carboxyphenylamino)-1,3,5-triazine-2,4-diyldiimino) diisophthalic acid), obtained via assemly reactions between Zn2+ and a semi-rigid pentacarboxylate ligand (L5-). Single-crystal X-ray diffraction analyses reveal that both compounds are three dimensional metal-organic frameworks (MOFs) built of the same {Zn2(CO2)5} molecular building blocks (MBBs) and L5- ligands but have different topologies (point symbols of (44•66) and (46•64)(46•64) for 1 and 2 respectively). The mechanisms of the selective and efficient quenching of their photoluminescence (PL) by a series of nitroaromatics (NACs) solutions could be explained by electron transfer, long range energy transfer and/or electrostatic interactions. Remarkablely, 1 and 2 can impressively detect the concentrations of dinoseb in solutions down to 0.09 and 0.11ppm respectively. Their PLs could also be quenched by nitrobenzene (NB) and 4-nitrotoluene (4-NT) vapors, and the emission from 2 can be more quickly quenched than that from 1 possibly due to 2’s larger pores and faster uptake of NAC vapors. 1 and 2 demonstrate significantly better performances than the two previously report 4-connected MOFs using Zn2+ and a ligand isomeric to L5- in detecting NACs in both suspensions and vapour mainly due to the ligands’ different LUMOs and arrangements of carboxylate groups.1 This work sheds lights on not only understanding of the formation of framework isomers but also the development of MOF-based NACs probes with better performances via judicious selections of proper ligands.

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Publication details

The article was received on 03 Feb 2017, accepted on 11 Apr 2017 and first published on 12 Apr 2017

Article type: Paper
DOI: 10.1039/C7CE00236J
Citation: CrystEngComm, 2017, Accepted Manuscript
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    Two (5, 5)-connected isomeric frameworks as highly selective and sensitive photoluminescent probes of nitroaromatics

    Y. Dai, H. Zhou, X. Song, J. Zhang, C. Hao, L. Di, Y. Wang, J. Ni and H. Wang, CrystEngComm, 2017, Accepted Manuscript , DOI: 10.1039/C7CE00236J

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