TY - JOUR

T1 - Solvatomorphism, CO2 adsorption and luminescence properties of non-aromatic bis-hydroxamate-based metal-organic frameworks

AU - Ushakov, Daniil A.

AU - Ryadun, Alexey A.

AU - Kovalenko, Konstantin A.

AU - Kirilyuk, Igor A.

AU - Demakov, Pavel A.

AU - Fedin, Vladimir P.

PY - 2025

Y1 - 2025

N2 - Two new Tb(iii) metal-organic frameworks with an aliphatic bis-hydroxamate linker have been synthesized and structurally characterized. The title compounds have [Tb2(H2O)2(OAc)2(L)2]·2Solv formulae, where L2− is a deprotonated form of 1,4-dihydroxy-3,3,6,6-tetramethylpiperazine-2,5-dione and Solv is N,N-dimethylacetamide or ethanol. Both compounds possess layered sql-type structures and appear to be solvatomorphic crystal phases, but with a significant change in the pore volume fraction from 35% for the DMA-based structure down to 23% for the EtOH-based one. The activation of the ethanol-based compound led to a porous network demonstrating hysteretic adsorption of carbon dioxide with a BET surface area of 493 m2 g−1. A narrow-banded emission in the green region, typical for Tb(iii)-based metal-organic complexes, was found for both obtained compounds with ca. 1% photoluminescence quantum yields, showing an ability of the first MOF-related example of a non-aromatic bis-hydroxamate strut presented herein to sensitize the phosphorescence of Tb(iii) ions.

AB - Two new Tb(iii) metal-organic frameworks with an aliphatic bis-hydroxamate linker have been synthesized and structurally characterized. The title compounds have [Tb2(H2O)2(OAc)2(L)2]·2Solv formulae, where L2− is a deprotonated form of 1,4-dihydroxy-3,3,6,6-tetramethylpiperazine-2,5-dione and Solv is N,N-dimethylacetamide or ethanol. Both compounds possess layered sql-type structures and appear to be solvatomorphic crystal phases, but with a significant change in the pore volume fraction from 35% for the DMA-based structure down to 23% for the EtOH-based one. The activation of the ethanol-based compound led to a porous network demonstrating hysteretic adsorption of carbon dioxide with a BET surface area of 493 m2 g−1. A narrow-banded emission in the green region, typical for Tb(iii)-based metal-organic complexes, was found for both obtained compounds with ca. 1% photoluminescence quantum yields, showing an ability of the first MOF-related example of a non-aromatic bis-hydroxamate strut presented herein to sensitize the phosphorescence of Tb(iii) ions.

UR - https://www.mendeley.com/catalogue/bf527647-779b-3538-bedd-b1c9dd78a426/

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-105008577889&origin=inward&txGid=df0c903f929da92ea02239d697cc2e3f

U2 - 10.1039/d5ce00383k

DO - 10.1039/d5ce00383k

M3 - Article

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

ER -