Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge

Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge Full article

Journal

Inorganics
ISSN: 2304-6740

Output data

Year: 2023, Volume: 11, Number: 6, Article number : 259, Pages count : 119 DOI: 10.3390/inorganics11060259

Authors

Demakov Pavel A. ¹ , Kovalenko Konstantin A. ¹ , Lavrov Alexander N. ¹ , Fedin Vladimir P. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia

Funding (1)

Ministry of Science and Higher Education of the Russian Federation

075-15-2022-263

Two new metal–organic frameworks based on highly flexible 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide (odabco) ligands were successfully synthesized and characterized. Their crystallographic formulae are [M(DMF)2(odabco)2](ClO4)2·dioxane, where M2+ = Co2+ (1) and Ni2+ (2), and DMF is N,N-dimethylformamide. The title compounds possess cationic 2D coordination networks filled with perchlorate anions and dioxane solvent molecules in the interlayer space, with 20% solvent accessible volume. Carbon dioxide adsorption measurements for desolvated samples 1a and 2a gave 511 m2/g and 377 m2/g specific surface areas, respectively, revealing the first example of gas adsorption properties in the structure based on a flexible odabco bridge, despite the presence of large counteranions within the positively charged network. Magnetization measurements for 1, 1a, 2 and 2a reveal their paramagnetic nature to be in a reasonable agreement with crystal structures, and almost no solvent dependence of the magnetization characteristics. A decrease in the effective magnetic moment observed at low temperatures is attributed mostly to zero-field level-splitting in the octahedral Ni2+ and Co2+ ions.

Demakov P.A. , Kovalenko K.A. , Lavrov A.N. , Fedin V.P.
Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge
Inorganics. 2023. V.11. N6. 259 :1-119. DOI: 10.3390/inorganics11060259 WOS Scopus OpenAlex

Submitted:	May 22, 2023
Published print:	Jun 17, 2023

Web of science:	WOS:001014611100001
Scopus:	2-s2.0-85163627951
OpenAlex:	W4381140678

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