TY - JOUR

T1 - Crystal structures, thermal and luminescent properties of gadolinium(Iii) trans-1,4-cyclohexanedicarboxylate metal-organic frameworks

AU - Demakov, Pavel A.

AU - Vasileva, Alena A.

AU - Lazarenko, Vladimir A.

AU - Ryadun, Alexey A.

AU - Fedin, Vladimir P.

N1 - Funding Information: Funding: The research was supported by the Ministry of Science and Higher Education of the Russian Federation, No. 121031700321-3 and No. 121031700321-8. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2021/11

Y1 - 2021/11

N2 - Four new gadolinium(III) metal-organic frameworks containing 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen) chelate ligands and trans-1,4-cyclohexanedicarboxylate (chdc2− ) were synthesized. Their crystal structures were determined by single-crystal X-ray diffraction analysis. All four coordination frameworks are based on the binuclear carboxylate building units. In the compounds [Gd2 (bpy)2 (chdc)3 ]·H2 O (1) and [Gd2 (phen)2 (chdc)3 ]·0.5DMF (2), the six-connected {Ln2 (L)2 (OOCR)6 } blocks form a 3D network with the primitive cubic (pcu) topology. In the compounds [Gd2 (NO3 )2 (phen)2 (chdc)2 ]·2DMF (3) and [Gd2 Cl2 (phen)2 (chdc)2 ]·0.3DMF·2.2dioxane (4), the four-connected {Ln2 (L)2 (X)2 OOCR)4 } units (where X = NO3− for 3 or Cl− for 4) form a 2D square-grid (sql) network. The solid-state luminescent properties were investigated for the synthesized frameworks. Bpy-containing compound 1 shows no luminescence, possibly due to the paramagnetic quenching by Gd3+ cation. In contrast, the phenathroline-containing MOFs 2–4 possess yellow emission under visible excitation (λex = 460 nm) with the tuning of the characteristic wavelength by the coordination environment of the metal center.

AB - Four new gadolinium(III) metal-organic frameworks containing 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen) chelate ligands and trans-1,4-cyclohexanedicarboxylate (chdc2− ) were synthesized. Their crystal structures were determined by single-crystal X-ray diffraction analysis. All four coordination frameworks are based on the binuclear carboxylate building units. In the compounds [Gd2 (bpy)2 (chdc)3 ]·H2 O (1) and [Gd2 (phen)2 (chdc)3 ]·0.5DMF (2), the six-connected {Ln2 (L)2 (OOCR)6 } blocks form a 3D network with the primitive cubic (pcu) topology. In the compounds [Gd2 (NO3 )2 (phen)2 (chdc)2 ]·2DMF (3) and [Gd2 Cl2 (phen)2 (chdc)2 ]·0.3DMF·2.2dioxane (4), the four-connected {Ln2 (L)2 (X)2 OOCR)4 } units (where X = NO3− for 3 or Cl− for 4) form a 2D square-grid (sql) network. The solid-state luminescent properties were investigated for the synthesized frameworks. Bpy-containing compound 1 shows no luminescence, possibly due to the paramagnetic quenching by Gd3+ cation. In contrast, the phenathroline-containing MOFs 2–4 possess yellow emission under visible excitation (λex = 460 nm) with the tuning of the characteristic wavelength by the coordination environment of the metal center.

KW - Coordination polymers

KW - Gadolinium

KW - Luminescence

KW - Metal-organic frameworks

KW - Rare earth elements

UR - http://www.scopus.com/inward/record.url?scp=85119614983&partnerID=8YFLogxK

U2 - 10.3390/cryst11111375

DO - 10.3390/cryst11111375

M3 - Article

AN - SCOPUS:85119614983

VL - 11

JO - Crystals

JF - Crystals

SN - 2073-4352

IS - 11

M1 - 1375

ER -