TY - JOUR

T1 - Low-dimensional coordination polymers based on cobalt(II) and aliphatic N,N’-dioxide: Syntheses, structures and spectroscopic characterization

AU - Abasheeva, Ksenia D.

AU - Demakov, Pavel A.

AU - Fedin, Vladimir P.

N1 - The authors are grateful to the Ministry of Science and Higher Education of the Russian Federation for financial support (Agreement No. 075-15-2022-263), providing an access to the large-scale research facility “EXAFS spectroscopy beamline”.

PY - 2024/11/1

Y1 - 2024/11/1

N2 - Four new coordination polymers based on cobalt(II) and 1,4-diazabicyclo[2.2.2]octane N,N’-dioxide (odabco) were successfully synthesized. According to single-crystal X-ray diffraction analysis results, their formulae are (Me2NH2)2[Co(odabco)(SO4)2] (1; Me2NH2+ = dimethylammonium), [Co(odabco)Cl2] (2), [Co(odabco)Br2] (3) and [Co(odabco)(OAc)2] (4; OAc− = acetate). All the compounds contain tetrahedral Co(II) ions coordinated by two odabco bridges and two additional terminal ligands, forming 1D polymeric chains. 2–4, containing monoanionic terminal ligands, possess almost similar zigzag chain structures, while 1, which is constructed by differently charged sulfate anion, possess notably different wavy anionic structure with small interchain voids. These voids are occupied by dimethylammonium cations, hydrogen-bonded to the coordination chains. Compounds 2–4 were characterized by powder X-ray diffraction, IR, and CHN methods, their thermal stability was evaluated by thermogravimetric analysis (TGA). Solid-state UV/Vis diffuse reflectance spectra were recorded for 2–4 and for a number of other Co(II)-odabco compounds reported by us previously. A comparative study for the representative series of chemically cognate CPs supported by DFT calculations, allowed to find reasonable dependencies between chemical nature of the ligand, metal center geometry and their spectral features.

AB - Four new coordination polymers based on cobalt(II) and 1,4-diazabicyclo[2.2.2]octane N,N’-dioxide (odabco) were successfully synthesized. According to single-crystal X-ray diffraction analysis results, their formulae are (Me2NH2)2[Co(odabco)(SO4)2] (1; Me2NH2+ = dimethylammonium), [Co(odabco)Cl2] (2), [Co(odabco)Br2] (3) and [Co(odabco)(OAc)2] (4; OAc− = acetate). All the compounds contain tetrahedral Co(II) ions coordinated by two odabco bridges and two additional terminal ligands, forming 1D polymeric chains. 2–4, containing monoanionic terminal ligands, possess almost similar zigzag chain structures, while 1, which is constructed by differently charged sulfate anion, possess notably different wavy anionic structure with small interchain voids. These voids are occupied by dimethylammonium cations, hydrogen-bonded to the coordination chains. Compounds 2–4 were characterized by powder X-ray diffraction, IR, and CHN methods, their thermal stability was evaluated by thermogravimetric analysis (TGA). Solid-state UV/Vis diffuse reflectance spectra were recorded for 2–4 and for a number of other Co(II)-odabco compounds reported by us previously. A comparative study for the representative series of chemically cognate CPs supported by DFT calculations, allowed to find reasonable dependencies between chemical nature of the ligand, metal center geometry and their spectral features.

KW - 1D structure

KW - Coordination polymer

KW - Crystal structure

KW - Diffuse reflectance

KW - Optical absorption

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85200166316&origin=inward&txGid=654557efb2a6f448b8641bbf46a3266f

UR - https://www.mendeley.com/catalogue/a0be9a24-7dee-3efa-93d2-aa66eed05298/

U2 - 10.1016/j.ica.2024.122288

DO - 10.1016/j.ica.2024.122288

M3 - Article

VL - 572

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

M1 - 122288

ER -