NDLI: Homo- and heterometallic luminescent 2-D stilbene metal–organic frameworks

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Homo- and heterometallic luminescent 2-D stilbene metal–organic frameworks

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Homo- and heterometallic luminescent 2-D stilbene metal–organic frameworks

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Vakil, Avinash Allendorf, Mark D. Jones, Simon C. Bauer, Christina A. Timofeeva, Tatiana V. Khrustalev, Victor N. Kinnibrugh, Tiffany L. Farrell, Richard A. Tongwa, Paul
Description	Author Affiliation: Bauer CA ( Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, CA 90095, USA.)
Abstract	Metal–organic frameworks (MOFs) can provide a matrix for the assembly of organic chromophores into well-defined geometries, allowing for tuning of the material properties and study of structure–property relationships. Here, we report on the effect of the coordinated metal ion on the luminescence properties of eight isostructural MOFs having the formula $M^{1}_{2}M^{2}L_{3}(DMF)_{2}$ $(M^{1}$ = $M^{2}$ = Zn (1), Cd (2), Mn (3), Co (4); $M^{1}$ = Zn, $M^{2}$ = Cd (5), Mn (6), Co (7); $M^{1}$ = Co, $M^{2}$ = Mn (8); L = trans-4,4′-stilbene dicarboxylate), synthesized by reaction of the appropriate metal nitrate or mixtures of metal nitrates with $LH_{2}$ in DMF. The crystal structures of 2, 3 and 5–8 were determined by X-ray diffraction to be composed of trinuclear metal clusters linked by stilbene dicarboxylate linkers in a paddlewheel geometry, extending to form a 2-D layered structure. In the mixed-metal cases, the larger metal ion was found to occupy the octahedral site in the cluster while the smaller ion occupies the tetrahedral positions, suggesting a selective, ligand-directed assembly process for the mixed-metal species. Variable temperature magnetic measurements for paramagnetic MOFs 3 and 6–8 were consistent with the site occupancies determined crystallographically, and indicated weak intra-cluster antiferromagnetic coupling for 3 and 8. Comparison between the crystal structures of 2, 3 and 5–8 and those reported for 1 and 4 in the literature reveal close resemblances between linker environments, with important intermolecular stilbene–stilbene geometries that are comparable in all cases. Interestingly, pale-colored 1–3 and 5–7 display very similar emission profiles upon excitation at $λ_{ex}$ = 350 nm, whereas dark-colored 4 and 8 do not exhibit detectable emission spectra. The bright, well-resolved luminescence of 1, 2 and 5 is ascribed to rigidification of the linker upon coordination to the $d^{10}$ metal ions, whereas the weaker emission observed for 3, 6 and 7 is presumably a result of quenching due to close proximity of the linker to one or more paramagnetic ions. Time-resolved measurements for 1, 2, 5 and 6 reveal biexponential emission decays, where the lifetime of the longer-lived state corresponds to observed variations in the nearest-neighbor cofacial stilbene–stilbene distances in their crystal structures. For 3, a monoexponential decay with shorter lifetime was determined, indicating significant paramagnetic quenching of its emissive state.
ISSN	14779226
Issue Number	7
Journal	Dalton Trans.
Volume Number	43
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2014-02-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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