Neutral Luminescent Metal-Organic Frameworks: Structural Diversification, Photophysical Properties, and Sensing Applications

Utilizing flexible bis­(tridentate)­polypyridyl ligands, the two new luminescent 2D metal organic frameworks {Zn₂(tpbn)­(2,6-NDC)₂}_n (1) and {[Zn₂(tphn)­(2,6-NDC)₂]·4H₂O}_n (2), where tpbn = N,N′,N″,N‴-tetrakis­(2-pyridylmethyl)-1,4-diaminobutane, tphn = N,N′,N″,N‴-tetrakis­(2-pyridylmethyl)-1,6-diaminohexane, and 2,6-H₂NDC = 2,6-naphthalenedicarboxylic acid, have been isolated in good yields under solvothermal conditions. Their solid-state molecular structures have been determined by single-crystal X-ray diffractometry. Both 1 and 2 have pentacoordinated Zn­(II) centers with an N₃O₂ environment from three nitrogen atoms of the tpbn or tphn ligand and two carboxylate oxygen atoms from two different 2,6-NDC linkers. However, the binding modes of the tridentate part of polypyridyl ligands to the Zn­(II) center are different in 1 and 2meridional (tpbn) vs facial (tphn) due to an increase (1.5 times) in the methylene chain length. Thus, the binding mode of 2,6-NDC to the Zn­(II) center differs: bis­(monodentate) syn-anti in 1 and bis­(monodentate) syn-syn in 2. This difference in binding modes of the components has a profound effect on the conformation of the six-membered ring (metal centers are considered as the vertices in it) within the 2D framework: honeycomb vs chair form for 1 and 2, respectively. In addition to further characterization by elemental analysis and UV–vis and FT-IR spectroscopy, their framework stabilities in water and thermal properties have been studied by powder X-ray diffraction and thermogravimetric analysis, respectively. On the basis of thermodiffractometry, 1 and 2 retain their crystallinity and overall structure up to 350 and 325 °C, respectively. Their luminescent properties have been utilized to demonstrate sensing of various solvents as well as nitro-aromatic compounds in water, which correlate well with their structural differences. Through the spectral overlap, lifetime measurements, and nature of the Stern–Volmer plots, the fluorescence quenching pathway for the nitro-analytes, particularly 2,4,6-trinitrophenol (TNP), is established for 1 and 2. Their recyclability and stability after sensing experiments are found to be excellent.