| Autor: |
Vasileva AA; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia. demakov@niic.nsc.ru.; Department of Natural Sciences, Novosibirsk State University, 2 Pirogova St., 630090 Novosibirsk, Russia., Demakov PA; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia. demakov@niic.nsc.ru., Guselnikova TY; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia. demakov@niic.nsc.ru., Ryadun AA; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia. demakov@niic.nsc.ru., Fedin VP; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia. demakov@niic.nsc.ru., Dybtsev DN; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia. demakov@niic.nsc.ru. |
| Abstrakt: |
Four new metal-organic frameworks with the formulae [Sm 2 (phen) 2 (NO 3 ) 2 (chdc) 2 ]·2solv, where solv = N , N -dimethylformamide (DMF; 1), N , N -dimethylacetamide (DMA; 2), N , N -diethylformamide (DEF; 3), N -formylpiperidine (NFP; 4), phen = 1,10-phenanthroline and chdc 2- = trans -1,4-cyclohexanedicarboxylate were synthesized and structurally characterized. These compounds are based on similar binuclear samarium(III)-carboxylate blocks, bound by flexible chdc linkers into layered sql -type coordination networks. The amide solvents drive different intralayer block orientations between 1 and 2-4 and different layer-to-layer packings in all the described compounds. A pronounced dependence of the emission color upon the excitation wavelength variation was determined for 1-4, while the relative impacts of Sm 3+ and phen emission on overall luminescence were found to depend strongly on these packings, and their reasonable correlation to the distances between the closest π-π-stacked phen moieties in the structures was revealed. Phase transitions between compounds 1-4 were studied by means of powder X-ray diffraction. Additionally, bimetallic near-white luminophores were obtained for phases 3 and 4 by doping their synthetic systems with a minor (∼5%) Tb 3+ additive. In general, this study shows a possibility of tuning the luminescence properties of porous metal-organic frameworks by minor structural differences induced by solvent-driven dynamics with no apparent quenching or other direct impact on the optical properties of the included solvent. |
