Mixed-valence outer-sphere RuII/RuIII ion-pair complexes. Synthesis, experimental, and theoretical studies

Impert O, Kozakiewicz-Piekarz A, Katafias A, Witwicki M, Komarnicka UK, Kurpiewska K, van Eldik R (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Polyhedron Elsevier

Book Volume: 223

Article Number: 115939

DOI: 10.1016/j.poly.2022.115939

Abstract

Two new ion-pair complexes, consisting of a cationic polypirydyl Ru(II) complex ([RuII(terpy)(bipy)Cl]+ or [RuII(terpy)(phen)Cl]+) and the cis-[RuIIICl2(pic)2]− anion (terpy = 2,2′:6′,2′′-terpyridine, bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline and pic− = picolinate) were synthesized. Magnetic and EPR studies were preceded by identifying the obtained species and checking the homogeneity and purity of the bulk material using various analytical techniques: single-crystal and powder X-ray diffraction, SEM, EDX, and FT-IR spectroscopies in the solid state, and ESI-MS in solution. The spectral characteristics in the UV–vis range and redox behavior of the ion-pair complexes were examined. The principal g components for [RuII(terpy)(bipy)Cl]+[cis-RuIIICl2(pic)2]−·(CH3)2CO·H2O, 1, and [RuII(terpy)(phen)Cl]+[cis-RuIIICl2(pic)2]−·2H2O, 2, and their RuIII precursor [H(Hpic)2]+[cis-RuIIICl2(pic)2]–∙2H2O were similar and typical for low-spin d5 species. The presence of one unpaired electron (in the dxy orbital) was shown by DFT calculations. The EPR spectra of 1 and 2 were characteristic for species in a singlet state (S = ½ systems) in contrast to that of their analog, previously reported for the first RuII/RuIII ion-pair complex, [RuII(bipy)2(pic)]+[cis-RuIIICl2(pic)2]−, typical for a species in the triplet state (S = 1 system).

Involved external institutions

Nicolaus Copernicus University (NCU) / Uniwersytet Mikołaja Kopernika w Toruniu (UMK) PL Poland (PL) University of Wroclaw / Uniwersytet Wrocławski PL Poland (PL) Jagiellonian University / Uniwersytet Jagielloński (UJ) PL Poland (PL)

How to cite

APA:

Impert, O., Kozakiewicz-Piekarz, A., Katafias, A., Witwicki, M., Komarnicka, U.K., Kurpiewska, K., & van Eldik, R. (2022). Mixed-valence outer-sphere RuII/RuIII ion-pair complexes. Synthesis, experimental, and theoretical studies. Polyhedron, 223. https://dx.doi.org/10.1016/j.poly.2022.115939

MLA:

Impert, Olga, et al. "Mixed-valence outer-sphere RuII/RuIII ion-pair complexes. Synthesis, experimental, and theoretical studies." Polyhedron 223 (2022).

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