TY - JOUR

T1 - Structural Diversity of Silver Fluorinated β-Diketonates: Effect of the Terminal Substituent and Solvent

AU - Vikulova, Evgeniia S.

AU - Sukhikh, Taisiya S.

AU - Gulyaev, Sergey A.

AU - Ilyin, Igor Yu

AU - Morozova, Natalia B.

N1 - Funding Information: Funding: This research was carried out with the support of the grant of the President of the Russian Federation for young scientists-candidates of sciences MK-6148.2021.1.3. The research was also supported by the Ministry of Science and Higher Education of the Russian Federation, N 121031700314-5 and 121031700313-8. Publisher Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2022/2/1

Y1 - 2022/2/1

N2 - In order to demonstrate the role of the fluorination and some solvents in the structural organization of the Ag(I) coordination polymers with β-diketonate ligands (R1C(O)CαHC(O)R2)− we synthesized a series of the compounds containing tfac-(R1 = CH3, R2 = CF3) and pfpac-(R1 = CH3, R2 = C2F5) anions. Solvent-free [Ag(L)]∞ (L = tfac 1, pfpac 2) compounds and the corresponding acetonitrile and toluene adducts have been characterized by elemental analysis and/or NMR, IR and single-crystal XRD. This series includes five new coordination polymers. Compound 1 is a 3D coordination framework based on Ag–Ochelate/bridge, Ag–Cα bonds, and argentophilic interactions. An increase in the fluorinated group leads to a chain coordination polymer 2 of an unusual structural organization. These chains can be represented as a “DNA-type”, where two intertwined helices based on Ag– Ochelate and Ag–Cα bonds are connected through Ag–Obridge ones. Two structural types of chain coordination polymers, [Ag(tfac)(CH3CN)] and [Ag2(L)2(solvent)], have been revealed for the adducts. The latter structural type differs significantly from the previously studied toluene and acetonitrile adducts of fluorinated Ag(I) β-diketonates of the same stoichiometry. Thermal analysis in helium showed that both 1 and 2 decompose to metallic silver with the compound of pfpac-ligand being slightly more stable.

AB - In order to demonstrate the role of the fluorination and some solvents in the structural organization of the Ag(I) coordination polymers with β-diketonate ligands (R1C(O)CαHC(O)R2)− we synthesized a series of the compounds containing tfac-(R1 = CH3, R2 = CF3) and pfpac-(R1 = CH3, R2 = C2F5) anions. Solvent-free [Ag(L)]∞ (L = tfac 1, pfpac 2) compounds and the corresponding acetonitrile and toluene adducts have been characterized by elemental analysis and/or NMR, IR and single-crystal XRD. This series includes five new coordination polymers. Compound 1 is a 3D coordination framework based on Ag–Ochelate/bridge, Ag–Cα bonds, and argentophilic interactions. An increase in the fluorinated group leads to a chain coordination polymer 2 of an unusual structural organization. These chains can be represented as a “DNA-type”, where two intertwined helices based on Ag– Ochelate and Ag–Cα bonds are connected through Ag–Obridge ones. Two structural types of chain coordination polymers, [Ag(tfac)(CH3CN)] and [Ag2(L)2(solvent)], have been revealed for the adducts. The latter structural type differs significantly from the previously studied toluene and acetonitrile adducts of fluorinated Ag(I) β-diketonates of the same stoichiometry. Thermal analysis in helium showed that both 1 and 2 decompose to metallic silver with the compound of pfpac-ligand being slightly more stable.

KW - Coordination polymers

KW - Crystal structure

KW - Fluorinated

KW - Silver

KW - TGA

KW - β-diketonate

UR - http://www.scopus.com/inward/record.url?scp=85123066702&partnerID=8YFLogxK

U2 - 10.3390/molecules27030677

DO - 10.3390/molecules27030677

M3 - Article

C2 - 35163942

AN - SCOPUS:85123066702

VL - 27

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 3

M1 - 677

ER -