TY - JOUR

T1 - Metal-organic frameworks with solvent-free lanthanide coordination environments

T2 - synthesis from aqueous ethanol solutions

AU - Litvinova, Yulia M.

AU - Gayfulin, Yakov M.

AU - Brylev, Konstantin A.

AU - Piryazev, Dmitry A.

AU - Van Leusen, Jan

AU - Kögerler, Paul

AU - Mironov, Yuri V.

N1 - Funding Information: The reported study was funded by the Russian Foundation for Basic Research (project 18-29-04007). The luminescence and magnetic measurements were supported by the grant of Russian Science Foundation (project 19-73-20196). The measurements were performed at the “Center for Optical and Laser Materials Research” (St. Petersburg State University, St. Petersburg, Russian Federation). Publisher Copyright: © 2020 The Royal Society of Chemistry. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/12/7

Y1 - 2020/12/7

N2 - A series of 12 new metal-organic frameworks based on lanthanide cations (Ln = Nd, Sm-Dy), octahedral cluster anions [Re6S8(CN)6]4- or [Re6Se8(CN)6]4- and adipamide (adp) were synthesized under mild conditions in aqueous ethanol solutions. Compounds of the general composition Cs[Ln(adp)2{Re6Q8(CN)6}]·3H2O (Ln = Nd, Sm-Dy; Q = S or Se) crystallize in the hexagonal space group P6422. Despite the presence of solvate H2O molecules in structure cavities, the crystal structures revealed that the coordination environment of lanthanide cations in these 3D polymers did not contain H2O ligands. This rare feature is attributed to the combination of a bulk cluster anion and flexible adp molecules, which occupy the lanthanide coordination sphere to yield a stable lanthanide-based building block. This assumption was confirmed by synthesis of a second crystalline modification of the compound Cs[Nd(adp)2{Re6S8(CN)6}]·3H2O (orthorhombic space group Cccm). Luminescence studies evidence the presence of the typical red luminescence of hexarhenium cluster complexes and the absence of observable luminescence of lanthanide cations for all the compounds except the Nd derivatives. Magnetic data indicate very weak antiferromagnetic exchange interactions between paramagnetic Ln3+ centers.

AB - A series of 12 new metal-organic frameworks based on lanthanide cations (Ln = Nd, Sm-Dy), octahedral cluster anions [Re6S8(CN)6]4- or [Re6Se8(CN)6]4- and adipamide (adp) were synthesized under mild conditions in aqueous ethanol solutions. Compounds of the general composition Cs[Ln(adp)2{Re6Q8(CN)6}]·3H2O (Ln = Nd, Sm-Dy; Q = S or Se) crystallize in the hexagonal space group P6422. Despite the presence of solvate H2O molecules in structure cavities, the crystal structures revealed that the coordination environment of lanthanide cations in these 3D polymers did not contain H2O ligands. This rare feature is attributed to the combination of a bulk cluster anion and flexible adp molecules, which occupy the lanthanide coordination sphere to yield a stable lanthanide-based building block. This assumption was confirmed by synthesis of a second crystalline modification of the compound Cs[Nd(adp)2{Re6S8(CN)6}]·3H2O (orthorhombic space group Cccm). Luminescence studies evidence the presence of the typical red luminescence of hexarhenium cluster complexes and the absence of observable luminescence of lanthanide cations for all the compounds except the Nd derivatives. Magnetic data indicate very weak antiferromagnetic exchange interactions between paramagnetic Ln3+ centers.

UR - http://www.scopus.com/inward/record.url?scp=85096959608&partnerID=8YFLogxK

U2 - 10.1039/d0ce01240h

DO - 10.1039/d0ce01240h

M3 - Article

AN - SCOPUS:85096959608

VL - 22

SP - 7935

EP - 7943

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 45

ER -