Alena A. Vasileva, Pavel A. Demakov, Tatiana Y. Guselnikova, Alexey A. Ryadun, Vladimir P Fedin, Danil N. Dybtsev
{"title":"Solvatomorphic Phase Transitions and Tunable Luminescence Emission in Lanthanide Metal-Organic Frameworks","authors":"Alena A. Vasileva, Pavel A. Demakov, Tatiana Y. Guselnikova, Alexey A. Ryadun, Vladimir P Fedin, Danil N. Dybtsev","doi":"10.1039/d4dt02613f","DOIUrl":null,"url":null,"abstract":"Four new metal-organic frameworks with the formulae [Sm<small><sub>2</sub></small>(phen)<small><sub>2</sub></small>(NO<small><sub>3</sub></small>)<small><sub>2</sub></small>(chdc)<small><sub>2</sub></small>]·2Solv, where Solv = N,N-dimethylformamide (DMF; <strong>1</strong>), N,N-dimethylacetamide (DMA; <strong>2</strong>), N,N-diethylformamide (DEF; <strong>3</strong>), N-formylpiperidine (NFP; <strong>4</strong>), phen = 1,10-phenanthroline and chdc<small><sup>2–</sup></small> = <em>trans</em>-1,4-cyclohexanedicarboxylate were synthesized and structurally characterized. These compounds are based on similar binuclear samarium(III)-carboxylate blocks, bound by flexible chdc linker into layered sql-type coordination networks. Different amide solvents drive different intralayer block orientations between <strong>1</strong> and <strong>2</strong>–<strong>4</strong> and different layer-to-layer packings in all the described compounds. A strong dependence of the emission color upon varying excitation wavelength was determined for <strong>1</strong>–<strong>4</strong>, while relative impacts of Sm<small><sup>3+</sup></small> and phen emission into overall luminescence were found to depend strongly on these packings, and their reasonable correlation to the distances between closest π-π-stacked phen moieties in the structures was revealed. Phase transitions between compounds <strong>1</strong>–<strong>4</strong> were studied by means of powder X-ray diffraction. Additionally, two-metal near-white luminophores were obtained for phases <strong>3</strong> and <strong>4</strong> by doping their synthetic systems by minor (~5%) additive of Tb<small><sup>3+</sup></small>. 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 of the optical properties of the solvent included.","PeriodicalId":3,"journal":{"name":"ACS Applied Electronic Materials","volume":null,"pages":null},"PeriodicalIF":4.3000,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Electronic Materials","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4dt02613f","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, ELECTRICAL & ELECTRONIC","Score":null,"Total":0}
引用次数: 0
Abstract
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 linker into layered sql-type coordination networks. Different amide solvents drive different intralayer block orientations between 1 and 2–4 and different layer-to-layer packings in all the described compounds. A strong dependence of the emission color upon varying excitation wavelength was determined for 1–4, while relative impacts of Sm3+ and phen emission into overall luminescence were found to depend strongly on these packings, and their reasonable correlation to the distances between 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, two-metal near-white luminophores were obtained for phases 3 and 4 by doping their synthetic systems by minor (~5%) additive of Tb3+. 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 of the optical properties of the solvent included.