The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals
The photodetachment of NO from [MII(CN5NO]2- with M = Fe, Ru, and Os, upon laser excitation at various wavelengths (355, 420, and 480 nm) was followed by various techniques. The three complexes showed a wavelength-dependent quantum yield of NO production Φ (NO), as measured with an NO-sensitive elec...
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2005
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1474905X_v4_n1_p75_Videla http://hdl.handle.net/20.500.12110/paper_1474905X_v4_n1_p75_Videla |
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paper:paper_1474905X_v4_n1_p75_Videla2023-06-08T16:17:46Z The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals iron complex nitric oxide osmium derivative ruthenium complex water absorption article chemical bond complex formation controlled study electrode enthalpy fluorescence spectroscopy hydrogen bond infrared spectroscopy laser induced optoacoustic spectroscopy low temperature procedures mathematical computing measurement photochemistry photon priority journal quantum yield spectral sensitivity spectroscopy temperature dependence ultraviolet spectrophotometry Cyanides Lasers Metals, Heavy Nitric Oxide Nitroso Compounds Organometallic Compounds Photochemistry Quantum Theory Spectrum Analysis Mus The photodetachment of NO from [MII(CN5NO]2- with M = Fe, Ru, and Os, upon laser excitation at various wavelengths (355, 420, and 480 nm) was followed by various techniques. The three complexes showed a wavelength-dependent quantum yield of NO production Φ (NO), as measured with an NO-sensitive electrode, the highest values corresponding to the larger photon energies. For the same excitation wavelength the decrease of Φ (NO) at 20 °C in the order Fe > Ru ≫ Os, is explained by the increasing M-N bond strength and inertness of the heavier metals. Transient absorption data at 420 nm indicate the formation of the [MIII(CN)5H2O]2- species in less than ca. 1 μs for M = Fe and Ru. The enthalpy content of [FeIII(CN)5H2O]2- with respect to the parent [FeII(CN)5NO]2- state is (190 ± 20) kJ mol-1, as measured by laser-induced optoacoustic spectroscopy (LIOAS) upon excitation at 480 nm. The production of [FeIII(CN5H2O]2- is concomitant with an expansion of (8 ± 3) ml mol-1 consistent with an expansion of the water bound through hydrogen bonds to the CN ligands plus the difference between NO release into the bulk and water entrance into the first coordination sphere. The activated process, as indicated by the relatively strong temperature dependence of the Φ (NO) values and by the temperature dependence of the appearance of the [FeIII(CN)5H2O]2- species, as determined by LIOAS, is attributed to NO detachment in less than ca. 100 ns from the isonitrosyl (ON) ligand (MS1 state). © The Royal Society of Chemistry and Owner Societies 2005. 2005 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1474905X_v4_n1_p75_Videla http://hdl.handle.net/20.500.12110/paper_1474905X_v4_n1_p75_Videla |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
iron complex nitric oxide osmium derivative ruthenium complex water absorption article chemical bond complex formation controlled study electrode enthalpy fluorescence spectroscopy hydrogen bond infrared spectroscopy laser induced optoacoustic spectroscopy low temperature procedures mathematical computing measurement photochemistry photon priority journal quantum yield spectral sensitivity spectroscopy temperature dependence ultraviolet spectrophotometry Cyanides Lasers Metals, Heavy Nitric Oxide Nitroso Compounds Organometallic Compounds Photochemistry Quantum Theory Spectrum Analysis Mus |
| spellingShingle |
iron complex nitric oxide osmium derivative ruthenium complex water absorption article chemical bond complex formation controlled study electrode enthalpy fluorescence spectroscopy hydrogen bond infrared spectroscopy laser induced optoacoustic spectroscopy low temperature procedures mathematical computing measurement photochemistry photon priority journal quantum yield spectral sensitivity spectroscopy temperature dependence ultraviolet spectrophotometry Cyanides Lasers Metals, Heavy Nitric Oxide Nitroso Compounds Organometallic Compounds Photochemistry Quantum Theory Spectrum Analysis Mus The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals |
| topic_facet |
iron complex nitric oxide osmium derivative ruthenium complex water absorption article chemical bond complex formation controlled study electrode enthalpy fluorescence spectroscopy hydrogen bond infrared spectroscopy laser induced optoacoustic spectroscopy low temperature procedures mathematical computing measurement photochemistry photon priority journal quantum yield spectral sensitivity spectroscopy temperature dependence ultraviolet spectrophotometry Cyanides Lasers Metals, Heavy Nitric Oxide Nitroso Compounds Organometallic Compounds Photochemistry Quantum Theory Spectrum Analysis Mus |
| description |
The photodetachment of NO from [MII(CN5NO]2- with M = Fe, Ru, and Os, upon laser excitation at various wavelengths (355, 420, and 480 nm) was followed by various techniques. The three complexes showed a wavelength-dependent quantum yield of NO production Φ (NO), as measured with an NO-sensitive electrode, the highest values corresponding to the larger photon energies. For the same excitation wavelength the decrease of Φ (NO) at 20 °C in the order Fe > Ru ≫ Os, is explained by the increasing M-N bond strength and inertness of the heavier metals. Transient absorption data at 420 nm indicate the formation of the [MIII(CN)5H2O]2- species in less than ca. 1 μs for M = Fe and Ru. The enthalpy content of [FeIII(CN)5H2O]2- with respect to the parent [FeII(CN)5NO]2- state is (190 ± 20) kJ mol-1, as measured by laser-induced optoacoustic spectroscopy (LIOAS) upon excitation at 480 nm. The production of [FeIII(CN5H2O]2- is concomitant with an expansion of (8 ± 3) ml mol-1 consistent with an expansion of the water bound through hydrogen bonds to the CN ligands plus the difference between NO release into the bulk and water entrance into the first coordination sphere. The activated process, as indicated by the relatively strong temperature dependence of the Φ (NO) values and by the temperature dependence of the appearance of the [FeIII(CN)5H2O]2- species, as determined by LIOAS, is attributed to NO detachment in less than ca. 100 ns from the isonitrosyl (ON) ligand (MS1 state). © The Royal Society of Chemistry and Owner Societies 2005. |
| title |
The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals |
| title_short |
The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals |
| title_full |
The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals |
| title_fullStr |
The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals |
| title_full_unstemmed |
The photorelease of nitrogen monoxide (NO) from pentacyanonitrosyl coordination compounds of group 8 metals |
| title_sort |
photorelease of nitrogen monoxide (no) from pentacyanonitrosyl coordination compounds of group 8 metals |
| publishDate |
2005 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1474905X_v4_n1_p75_Videla http://hdl.handle.net/20.500.12110/paper_1474905X_v4_n1_p75_Videla |
| _version_ |
1768545617011802112 |