Universität zu Köln

Garci, Fatma, Chebbi, Hammouda, Rouzbeh, Nahal, Rochels, Leonhard, Disch, Sabrina ORCID: 0000-0002-4565-189X, Klein, Axel and Zid, Mohamed Faouzi (2022). Structure, optical and magnetic properties of the pyridinium cobaltate (C6H9N2)(2)[CoCl4]. Inorg. Chim. Acta, 539. LAUSANNE: ELSEVIER SCIENCE SA. ISSN 1873-3255

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Abstract

The reaction of 2-amino-4-methylpyridine (L) with CoCl2 center dot 6H(2)O in hydrochloric acid gave the chlorocobaltate (HL)(2)[CoCl4] in 82% yield. X-ray diffraction of the blue crystalline material showed isolated [CoCl4](2-) tetrahedra in the structure, connected to the aromatic 2-amino-4-methyl pyridinium cations through H bonding while the cations show pi-stacking. FT-IR spectroscopy in conjunction with Hirshfeld surface analysis confirmed the importance of the 2-amino function in the cations for the hydrogen bonding. The material is thermally stable up to 270 degrees C. Intense UV-vis absorptions in the range 200-400 nm were assigned to pi-pi* transitions in the pyridinium cation, weaker features in the range 600-750 nm were due to ligand-field transitions in the d(7) high-spin system [CoCl4](2-). Excitation at 370 nm led to an intense blue-green emission at lambda(em) = 473 nm attributable to excited p-p* states. The molar susceptibility measured over a range of 5-300 K reveals paramagnetic behavior at high temperature range with an effective magnetic moment of mu(eff) = 4.74 mu B indicating a significant spin-orbit coupling contribution adding to the spin-only value of 3.87 mu B expected for Co(II) with 3d(7) high spin configuration.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Garci, Fatma UNSPECIFIED UNSPECIFIED UNSPECIFIED Chebbi, Hammouda UNSPECIFIED UNSPECIFIED UNSPECIFIED Rouzbeh, Nahal UNSPECIFIED UNSPECIFIED UNSPECIFIED Rochels, Leonhard UNSPECIFIED UNSPECIFIED UNSPECIFIED Disch, Sabrina UNSPECIFIED orcid.org/0000-0002-4565-189X UNSPECIFIED Klein, Axel UNSPECIFIED UNSPECIFIED UNSPECIFIED Zid, Mohamed Faouzi UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-675490
DOI:	10.1016/j.ica.2022.121003
Journal or Publication Title:	Inorg. Chim. Acta
Volume:	539
Date:	2022
Publisher:	ELSEVIER SCIENCE SA
Place of Publication:	LAUSANNE
ISSN:	1873-3255
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language CRYSTAL-STRUCTURE; HYDROCHLORIC-ACID; HYDROGEN-BOND; COMPLEXES; COBALT(II); PEROVSKITES; COPPER(II); LIGAND; RANGE Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/67549