Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization
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...
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2015
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v44_n39_p17064_Maisuls http://hdl.handle.net/20.500.12110/paper_14779226_v44_n39_p17064_Maisuls |
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paper:paper_14779226_v44_n39_p17064_Maisuls2025-07-30T18:53:56Z Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization Absorption spectroscopy Crystal atomic structure Density functional theory Ground state Ligands Mass spectrometry Spectrometry Synthesis (chemical) Ultraviolet spectroscopy X ray diffraction 1 ,10-phenanthroline Electronic transition Ground state geometry Spectrometry technique Spectroscopic characterization Trifluoromethanesulfonate UV-VIS absorption spectra X ray structural analysis Rhenium compounds beta carboline carboline derivative rhenium chemical structure chemistry infrared spectroscopy mass spectrometry procedures ultraviolet spectrophotometry X ray diffraction Carbolines Molecular Structure Rhenium Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization Spectrophotometry, Ultraviolet Spectroscopy, Fourier Transform Infrared X-Ray Diffraction 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. © The Royal Society of Chemistry 2015. 2015 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v44_n39_p17064_Maisuls http://hdl.handle.net/20.500.12110/paper_14779226_v44_n39_p17064_Maisuls |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Absorption spectroscopy Crystal atomic structure Density functional theory Ground state Ligands Mass spectrometry Spectrometry Synthesis (chemical) Ultraviolet spectroscopy X ray diffraction 1 ,10-phenanthroline Electronic transition Ground state geometry Spectrometry technique Spectroscopic characterization Trifluoromethanesulfonate UV-VIS absorption spectra X ray structural analysis Rhenium compounds beta carboline carboline derivative rhenium chemical structure chemistry infrared spectroscopy mass spectrometry procedures ultraviolet spectrophotometry X ray diffraction Carbolines Molecular Structure Rhenium Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization Spectrophotometry, Ultraviolet Spectroscopy, Fourier Transform Infrared X-Ray Diffraction |
| spellingShingle |
Absorption spectroscopy Crystal atomic structure Density functional theory Ground state Ligands Mass spectrometry Spectrometry Synthesis (chemical) Ultraviolet spectroscopy X ray diffraction 1 ,10-phenanthroline Electronic transition Ground state geometry Spectrometry technique Spectroscopic characterization Trifluoromethanesulfonate UV-VIS absorption spectra X ray structural analysis Rhenium compounds beta carboline carboline derivative rhenium chemical structure chemistry infrared spectroscopy mass spectrometry procedures ultraviolet spectrophotometry X ray diffraction Carbolines Molecular Structure Rhenium Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization Spectrophotometry, Ultraviolet Spectroscopy, Fourier Transform Infrared X-Ray Diffraction Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization |
| topic_facet |
Absorption spectroscopy Crystal atomic structure Density functional theory Ground state Ligands Mass spectrometry Spectrometry Synthesis (chemical) Ultraviolet spectroscopy X ray diffraction 1 ,10-phenanthroline Electronic transition Ground state geometry Spectrometry technique Spectroscopic characterization Trifluoromethanesulfonate UV-VIS absorption spectra X ray structural analysis Rhenium compounds beta carboline carboline derivative rhenium chemical structure chemistry infrared spectroscopy mass spectrometry procedures ultraviolet spectrophotometry X ray diffraction Carbolines Molecular Structure Rhenium Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization Spectrophotometry, Ultraviolet Spectroscopy, Fourier Transform Infrared X-Ray Diffraction |
| description |
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. © The Royal Society of Chemistry 2015. |
| title |
Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization |
| title_short |
Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization |
| title_full |
Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization |
| title_fullStr |
Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization |
| title_full_unstemmed |
Norharmane rhenium(i) polypyridyl complexes: Synthesis, structural and spectroscopic characterization |
| title_sort |
norharmane rhenium(i) polypyridyl complexes: synthesis, structural and spectroscopic characterization |
| publishDate |
2015 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v44_n39_p17064_Maisuls http://hdl.handle.net/20.500.12110/paper_14779226_v44_n39_p17064_Maisuls |
| _version_ |
1840321924587061248 |