TY - JOUR

T1 - Structures and Luminescent Properties of Rare-Earth Metal–Organic Framework Series with Thieno[3,2b]thiophene-2,5-dicarboxylate

AU - Yudina, Yuliya A.

AU - Demakov, Pavel A.

AU - Ryadun, Alexey A.

AU - Fedin, Vladimir P.

AU - Dybtsev, Danil N.

N1 - Funding Information: The research was supported by Russian Science Foundation, project № 18-13-00203, https://rscf.ru/project/18-13-00203/ (accessed at 27 September 2022). The analytical services were supported by the Ministry of Science and Higher Education of the Russian Federation, projects № 121031700321-3 and 121031700313-8. Publisher Copyright: © 2022 by the authors.

PY - 2022/10

Y1 - 2022/10

N2 - Four new rare-earth metal–organic frameworks containing thieno[3,2b]thiophene-2,5-dicarboxylate (ttdc2−) with general formulae [M2(DMF)4(ttdc)3] (M3+ = Y3+ for 1, La3+ for 2, Tb3+ for 3) and [M2(H2O)2(ttdc)3] (M3+ = Lu3+ for 4) were synthesized. Their crystal structures were determined by performing a single-crystal X-ray diffraction analysis. Coordination polymers 1–3 are based on the binuclear metal-carboxylate building units with the formulae {M2(DMF)4(OOCR)6}. The six-connected blocks in 1–3 form a three-dimensional network with the primitive cubic (pcu) topology. Coordination framework 4 is based on chains comprised by stretched pseudo-binuclear metal-carboxylate building units. The chains are interconnected in four directions with ttdc2− linkers forming the 3D framework. The luminescent properties were studied for the synthesized frameworks in the solid state. All the coordination frameworks show a broad blue emission band (λex = 380 nm) typical for intra-ligand electron transitions. The sensing properties of 3 dispersions in solutions were investigated in detail and the luminescent response (quenching) was discovered in the presence of cinnamaldehyde and quinoline in diluted solutions at concentrations of as low as 4 × 10−1 vol.% and 4 × 10−2 vol.% (~3 × 10−3 M), respectively.

AB - Four new rare-earth metal–organic frameworks containing thieno[3,2b]thiophene-2,5-dicarboxylate (ttdc2−) with general formulae [M2(DMF)4(ttdc)3] (M3+ = Y3+ for 1, La3+ for 2, Tb3+ for 3) and [M2(H2O)2(ttdc)3] (M3+ = Lu3+ for 4) were synthesized. Their crystal structures were determined by performing a single-crystal X-ray diffraction analysis. Coordination polymers 1–3 are based on the binuclear metal-carboxylate building units with the formulae {M2(DMF)4(OOCR)6}. The six-connected blocks in 1–3 form a three-dimensional network with the primitive cubic (pcu) topology. Coordination framework 4 is based on chains comprised by stretched pseudo-binuclear metal-carboxylate building units. The chains are interconnected in four directions with ttdc2− linkers forming the 3D framework. The luminescent properties were studied for the synthesized frameworks in the solid state. All the coordination frameworks show a broad blue emission band (λex = 380 nm) typical for intra-ligand electron transitions. The sensing properties of 3 dispersions in solutions were investigated in detail and the luminescent response (quenching) was discovered in the presence of cinnamaldehyde and quinoline in diluted solutions at concentrations of as low as 4 × 10−1 vol.% and 4 × 10−2 vol.% (~3 × 10−3 M), respectively.

KW - coordination polymers

KW - lanthanide contraction

KW - luminescence

KW - metal–organic frameworks

KW - rare earth elements

KW - sensing

UR - http://www.scopus.com/inward/record.url?scp=85140728989&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/d5246e0e-05c8-32c0-8c0a-bac13be9caa2/

U2 - 10.3390/cryst12101374

DO - 10.3390/cryst12101374

M3 - Article

AN - SCOPUS:85140728989

VL - 12

JO - Crystals

JF - Crystals

SN - 2073-4352

IS - 10

M1 - 1374

ER -