Azo–hydrazone tautomerism in organometallic complexes triggered by a -Re(CO)3(L) core: A spectroscopic and theoretical study

Maldonado, Tamara; Flores, Erick; Llanos, Leonel; Aravena, Daniel; Vega, Andrés; Godoy, Fernando; Aspée, Alexis; Arancibia-Miranda, Nicolás; Ferraudi, Guillermo; Gómez, Alejandra

doi:10.1016/j.dyepig.2021.109953

Azo–hydrazone tautomerism in organometallic complexes triggered by a -Re(CO)₃(L) core: A spectroscopic and theoretical study

Journal Article · Thu Nov 18 23:00:00 EST 2021 · Dyes and Pigments

DOI:https://doi.org/10.1016/j.dyepig.2021.109953· OSTI ID:1977066

^[1]; Flores, Erick ^[2]; ^[2]; ^[2]; Vega, Andrés ^[3]; Godoy, Fernando ^[2]; Aspée, Alexis ^[2]; Arancibia-Miranda, Nicolás ^[2]; Ferraudi, Guillermo ^[4]; Gómez, Alejandra ^[2]

Universidad de Santiago de Chile (Chile); OSTI
Universidad de Santiago de Chile (Chile)
Universidad Andres Bello, Viña del Mar (Chile)
University of Notre Dame, IN (United States). Notre Dame Radiation Laboratory (NDRL)

The spectroscopic properties and tautomeric behavior of five novel Rhenium (I) tricarbonyl complexes bearing an azo ligand are presented. The organic ligand is stable in solution as the hydrazone tautomer. It remains as hydrazone in different medium conditions (solvent, concentration, pH, etc.) without the formation of detectable amounts of the azo tautomer. However, the complexation of this ligand to the strong electron-withdrawing fragment -Re(CO)₃X (X = Cl^–, Br^–) causes tautomerism to appear in the organic moiety. Two well-defined regions in the electronic spectra for both tautomers were observed, allowing the azo/enol-keto/hydrazone equilibrium to be followed. TD-DFT calculations indicate that for the keto/hydrazone form, the main absorption band is attributed to an IL transition. In contrast, the azo/enol species shows a major contribution of the ¹MLCT (dπ(Re) → dπ*(NN)) transition. The tautomeric equilibrium is easily shifted using solvents with different dielectric constant and hydrogen bond donor/acceptor (HBD/HBA) abilities. Also, the tautomerization process is deeply influenced by the electronic properties of the axial ligand. Therefore, this behavior represents a different strategy for the design of novel materials with optical properties. Furthermore, tautomerism is affected by the concentration of complexes and the presence of water in solvents. Finally, the acid-base behavior of these compounds in a 50% v/v ethanol-buffer system showed that the azo/enol tautomer is stabilized in acidic media. At the same time, an increase of pH promotes tautomerization toward the keto/hydrazone, followed by forming the anionic form at pH > 8.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FC02-04ER15533

OSTI ID:: 1977066

Alternate ID(s):: OSTI ID: 1868624

Journal Information:: Dyes and Pigments, Journal Name: Dyes and Pigments Journal Issue: C Vol. 197; ISSN 0143-7208

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Azo–hydrazone tautomerism in organometallic complexes triggered by a -Re(CO)3(L) core: A spectroscopic and theoretical study

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Azo–hydrazone tautomerism in organometallic complexes triggered by a -Re(CO)₃(L) core: A spectroscopic and theoretical study