INIFTA   05425
INSTITUTO DE INVESTIGACIONES FISICO-QUIMICAS TEORICAS Y APLICADAS
Unidad Ejecutora - UE
artículos
Título:
Norharmane rhenium(I) polypyridyl complexes: synthesis, structural and spectroscopic characterization
Autor/es:
IVÁN MAISULS; EZEQUIEL WOLCAN; OSCAR E. PIRO; GUSTAVO A. ETCHEVERRÍA; GABRIELA PETROSELLI; ROSA ERRA-BALLSELS; FRANCO M. CABRERIZO; GUSTAVO T. RUIZ
Revista:
DALTON TRANSACTIONS
Editorial:
ROYAL SOC CHEMISTRY
Referencias:
Lugar: Cambridge; Año: 2015 vol. 44 p. 17064 - 17074
ISSN:
1477-9226
Resumen:
Two novel Re(I) complexes with the general formula fac-[Re(CO)3(L)(nHo)]CF3SO3, where L= 2,2? bipyridine (bpy) or 1,10 phenanthroline (phen) and nHo (9H-pyrido[3,4-b]indole; norharmane) have been synthesized. The Re(I)-nHo complexes were characterized by structural X-ray diffraction, 1H and 13C NMR, UV-vis absorption and FT-IR spectroscopy, and by a combination of two mass spectrometry techniques, namely ESI-MS and UV-MALDI-MS. All characterizations showed that nHo is coordinated to the metal atom by the pyridine nitrogen of the molecule. X-ray structural analysis revealed that the crystal lattices for both complexes are further stabilized by a strong >N-H???O bond between the pyrrole NH group of the pyridoindole ligand and one oxygen atom of the trifluoromethanesulfonate counter-ion. Ground state geometry optimization by DFT calculations showed that in fluid solution the nHo ligand may rotate freely. The nature of the electronic transitions of Re(CO)3(bpy)(nHo)+ were established by TD-DFT calculations. The set of the most important electronic transitions present in this complex are comprised of π→π* electronic transitions centered on bpy and nHo moieties, LLCTnHo→COs, MLLCTRe(CO)3→bpy and LLCTnHo→bpy transitions. Additionally, TD-DFT calculations predict the existence of another two intense MLLCTRe(CO)3→nHo electronic transitions. Calculated UV-vis absorption spectra are in good agreement with the corresponding experimental data for the bpy-containing complex.