Bipyridine-Based Nanosized Metal–Organic Framework with Tunable Luminescence by a Postmodification with Eu(III): An Experimental and Theoretical Study

Abstract

A gallium 2,2′-bipyridine-5,5′-dicarboxylate metal–organic framework, Ga­(OH)­(bpydc), denoted as COMOC-4 (COMOC = Center for Ordered Materials, Organometallics and Catalysis, Ghent University) has been synthesized via solvothermal synthesis procedure. The structure has the topology of an aluminum 2,2′-bipyridine-5,5′-dicarboxylate – the so-called MOF-253. TEM and SEM micrographs show the COMOC-4 crystals are formed in nanoplates with uniform size of 30–50 nm. The UV–vis spectra of COMOC-4 in methanol solution show maximal electronic absorption at 307 nm. This results from linker to linker transitions as elucidated by time-dependent density functional theory simulations on the linker and COMOC-4 cluster models. When excited at 400 nm, COMOC-4 displays an emission band centered at 542 nm. Upon immersion in different solvents, the emission band for the framework is shifted in the range of 525–548 nm depending on the solvent. After incorporating Eu³⁺ cations, the emission band of the framework is shifted to even shorter wavelengths (505 nm). By varying the excitation wavelengths from 250 to 400 nm, we can fine-tune the emission from red to yellowish green in the CIE diagram. The luminescence behavior of Eu³⁺ cations is well preserved and the solid-state luminescence lifetimes of τ₁ = 45 μs (35.4%) and τ₂ = 162 μs (64.6%) are observed