TY - JOUR

T1 - Solvatomorphic phase transitions and tunable luminescence emission in lanthanide metal-organic frameworks

AU - Vasileva, Alena A.

AU - Demakov, Pavel A.

AU - Guselnikova, Tatiana Y.

AU - Ryadun, Alexey A.

AU - Fedin, Vladimir P.

AU - Dybtsev, Danil N.

N1 - The research was supported by the Russian Science Foundation, project No. 23-13-00310.

PY - 2024/11/24

Y1 - 2024/11/24

N2 - Four new metal-organic frameworks with the formulae [Sm2(phen)2(NO3)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 chdc2− = 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 Sm3+ 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%) Tb3+ 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.

AB - Four new metal-organic frameworks with the formulae [Sm2(phen)2(NO3)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 chdc2− = 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 Sm3+ 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%) Tb3+ 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.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85209709511&origin=inward&txGid=3312d1ae0075a195c2074894bf544302

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001357806900001

UR - https://www.mendeley.com/catalogue/6552a607-e066-3893-a99b-ddd6c413fd20/

U2 - 10.1039/d4dt02613f

DO - 10.1039/d4dt02613f

M3 - Article

C2 - 39560504

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

ER -