Abstract
Metal complexes with ligands that coordinate via the nitrogen atom of azo (N?N) or imino (C?N) groups are of interest due to their ?-acceptor properties and redox-active nature, which leads to interesting (opto)electronic properties and reactivity. Here, we describe the synthesis and characterization of rhenium(I) tricarbonyl complexes with neutral N,N-bidentate formazans, which possess both N?N and C?N fragments within the ligand backbone (Ar1-NH-N?C(R3)-N?N-Ar5). The compounds were synthesized by reacting equimolar amounts of [ReBr(CO)5] and the corresponding neutral formazan. X-ray crystallographic and spectroscopic (IR, NMR) characterization confirmed the generation of formazan-type species with the structure fac-[ReBr(CO)3(κ2-N2,N4(Ar1-N1H-N2?C(R3)-N3?N4-Ar5))]. The formazan ligand coordinates the metal center in the ‘open' form, generating a five-membered chelate ring with a pendant NH arm. The electronic absorption and emission properties of these complexes are governed by the presence of low-lying ?*-orbitals on the ligand as shown by DFT calculations. The high orbital mixing between the metal and ligand results in photophysical properties that contrast to those observed in fac-[ReBr(CO)3(L,L)] species with α-diimine ligands.
Original language | English |
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Pages (from-to) | 13532-13542 |
Number of pages | 11 |
Journal | Inorganic Chemistry |
Volume | 61 |
Issue number | 34 |
DOIs | |
Publication status | Published - 29-Aug-2022 |
Datasets
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CCDC 2181177: Experimental Crystal Structure Determination
van Vliet, S. (Contributor), Alachouzos, G. (Contributor), de Vries, F. (Contributor), Pfeifer, L. (Contributor) & Feringa, B. L. (Contributor), Cambridge Crystallographic Data Centre, 22-Jun-2022
DOI: 10.5517/ccdc.csd.cc2c6pkv
Dataset
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CCDC 2180752: Experimental Crystal Structure Determination
Capulin Flores, L. (Contributor), Paul, L. A. (Contributor), Siewert, I. (Contributor), Havenith, R. (Contributor), Zúñiga-Villarreal, N. (Contributor) & Otten, E. (Contributor), Cambridge Crystallographic Data Centre, 21-Jun-2022
DOI: 10.5517/ccdc.csd.cc2c67vp
Dataset
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CCDC 2180754: Experimental Crystal Structure Determination
Capulin Flores, L. (Contributor), Paul, L. A. (Contributor), Siewert, I. (Contributor), Havenith, R. (Contributor), Zúñiga-Villarreal, N. (Contributor) & Otten, E. (Contributor), Cambridge Crystallographic Data Centre, 21-Jun-2022
DOI: 10.5517/ccdc.csd.cc2c67xr
Dataset