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Cationic and neutral copper(I) iodide cluster MOFs derived from tridentate N-donor functionalized P(V) ligands: synthesis, structure and photophysical properties

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Abstract

Formation of cationic and neutral CuI cluster MOFs have been reported starting from tridentate phosphoramide ligands, [\(\hbox {(NHR)}_{3}\hbox {P}=\hbox {E}\)] (\(\hbox {L}^{1}\): \(\hbox {R} = \hbox {3-aminoquinolinyl (AQ)}\), \(\hbox {E} = \hbox {S}\); \(\hbox {L}^{2}\): \(\hbox {R} = \hbox {3-pyridyl (PY)}\), \(\hbox {E} = \hbox {S}\); \(\hbox {L}^{3}\): \(\hbox {R} = \hbox {3-aminoquinolinyl (AQ)}\), \(\hbox {E} = \hbox {O}\)). By utilizing \(\hbox {L}^{1}\), a cationic 2D-MOF \(\{[(\hbox {L}^{1})_{2}\hbox {(Cu}_{6}\hbox {I}_{5})]\hbox {(OH)}\cdot \hbox {3DMF}\cdot \hbox {4MeOH}\}_{\mathrm{n}}\), 1 containing a rugby ball shaped discrete \(\hbox {Cu}_{6}\hbox {I}_{5}\) cluster has been reported earlier. Formation of a new 3D-MOF \(\{[(\hbox {L}^{2})_{2}(\hbox {Cu}_{6}\hbox {I}_{4})]\hbox {(OH)}_{2}\cdot \hbox {2DMF}\}_{\mathrm{n}}\) containing a Zintl type \([(\hbox {Cu}_{6}\hbox {I}_{4})^{2+}]_{\mathrm{n}}\) cluster chains is reported in this paper. A neutral cluster MOFs 3 with formula unit of \(\{[\hbox {Cu}_{4}\hbox {I}_{4}\hbox {L}^{3}(\hbox {CH}_{3}\hbox {CN})]\cdot \hbox {2DMF}\cdot 3\hbox {H}_{2}\hbox {O}\}_{\mathrm{n}}\) has been prepared from the ligand \(\hbox {L}^{3}\). Formation of the smaller \(\hbox {Cu}_{4}\hbox {I}_{4}\) clusters in the MOF 3 is due to the presence of a MeCN ligation at one of the Cu(I) atoms which not only precludes the extension of the assembly in three dimension but also reduces the size of the obtained cluster. Unlike 1 which showed a ligand-assisted thermochromism, photophysical studies on the 3D-MOF 2 exhibited green phosphorescence at both 298 K and 77 K. The occurrence of the phosphorescence at 77 K in 2 is due to triplet cluster centered (\({}^3\hbox {CC}\)) excited state of the cluster as there is no ligand-centered transition observed at 298 K. The 2D-MOF 3 does not show any characteristic luminescence behavior as the presence of the acetonitrile coordination at one of the Cu(I) ion is believed to quench the emission by non-radiative pathways. Further, luminescence quenching experiments on 1 and 2 with aromatic nitro-analytes showed a very high sensing selectivity for picric acid (TNP) over other aromatic nitro-analytes.

Graphical Abstract

SYNOPSIS: Employing tridentate phosphoramide ligands containing 3-aminoquinolyl and 3-pyridyl moieties, new examples of cluster MOFs containing cationic and neutral copper(I) iodide clusters were prepared. The MOF 2 contains a rugby ball-shaped, edge-fused polymeric \(\{[\hbox {Cu}_{6}\hbox {I}_{4}]^{2+}\}_{\mathrm{n}}\) clusters, whereas the MOF 3 contains a cubane-type discrete \(\hbox {Cu}_{4}\hbox {I}_{4}\) neutral cluster. Photophysical studies on the cationic complexes showed interesting phosphorescence emission and selective detection of picric acid.

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Acknowledgements

This work was supported by SERB, India via Grant No. EMR/2016/000614 (R.B.). A.Y. thanks the CSIR, India and M.S.D. thanks the UGC, India for the fellowship. The High Energy Materials Research Laboratory, Pune is acknowledged for providing the samples of the Nitroaromatic compounds to IISER, Pune.

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  1. Department of Chemistry, Indian Institute of Science Education and Research (IISER), Pune, Dr. Homi Bhabha Road, Pune, Maharashtra, 411 008, India

    Ashok Yadav, Mahesh S Deshmukh & Ramamoorthy Boomishankar

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  1. Ashok Yadav
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Correspondence to Ramamoorthy Boomishankar.

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Dedicated to Prof. K C Kumara Swamy on the occasion of his $$60^{\mathrm{th}}$$ 60 th Birthday.

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Yadav, A., Deshmukh, M.S. & Boomishankar, R. Cationic and neutral copper(I) iodide cluster MOFs derived from tridentate N-donor functionalized P(V) ligands: synthesis, structure and photophysical properties. J Chem Sci 129, 1093–1103 (2017). https://doi.org/10.1007/s12039-017-1284-4

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