FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2024372298> ?p ?o ?g. }

• W2024372298 endingPage "668" @default.
• W2024372298 startingPage "661" @default.
• W2024372298 abstract "Several clusters Os3(CO)10(α-diimine) (α-diimine = pyridine-2-carbaldehyde N-R-imine or 1,4-di-R-1,4-diazabutadiene) were synthesized and studied with respect to their spectroscopic and photochemical properties. According to the resonance Raman spectra the visible absorption band of these clusters belongs to electronic transitions having Os-to-α-diimine charge transfer (MLCT) character with a variable degree of π-delocalization within the Os(α-diimine) moiety. Upon irradiation into these transitions zwitterions -Os(CO)4−Os(CO)4−Os+(S)(CO)2(α-diimine) are formed in coordinating solvents (S) and biradicals •Os(CO)4−Os(CO)4−Os+(CO)2(α-diimine•-) in noncoordinating solvents and in THF at ambient temperature. The zwitterions live seconds in nitrile solvents and minutes in pyridine, and they largely regenerate the parent clusters. Quantum yields of zwitterion formation are wavelength independent and range from 10-2 to 3 × 10-2 with an activation energy varying from 440 to 720 cm-1. For one of the clusters the quantum yield of zwitterion formation in pyridine was studied in dependence of applied pressure. The activation volume ΔV‡ = +7.0 ± 0.5 cm3 mol-1 derived from these measurements indicates that the effect of bond cleavage is partially offset by coordination of the solvent. In apolar solvents biradicals are formed instead of zwitterions, which could be detected with nanosecond time-resolved absorption spectroscopy, while their adducts with nitrosodurene were observed with EPR spectroscopy. Their lifetimes vary from 5 ns to 1 μs depending on the solvent and the α-diimine. The biradicals transform into zwitterions in the presence of a Lewis base. In addition, they produce with low efficiency an isomeric product in which the α-diimine bridges between two Os atoms. The formation of very similar photoproducts (biradicals, α-diimine-bridged isomeric products, charge-separated species) as in the case of binuclear metal−metal-bonded complexes such as (CO)5MnMn(CO)3(α-diimine) points to the occurrence of a primary photoprocess in which an Os−Os bond is broken homolytically. This reaction most likely occurs from a reactive 3σπ* state after surface crossing from the unreactive but optically accessible MLCT states." @default.
• W2024372298 created "2016-06-24" @default.
• W2024372298 creator A5014875669 @default.
• W2024372298 creator A5024617682 @default.
• W2024372298 creator A5042128219 @default.
• W2024372298 creator A5067584431 @default.
• W2024372298 creator A5076429234 @default.
• W2024372298 creator A5080879830 @default.
• W2024372298 date "1998-01-28" @default.
• W2024372298 modified "2023-10-16" @default.
• W2024372298 title "Photochemistry of the Triangular Clusters Os₃(CO)₁₀(α-diimine): Homolysis of an Os−Os Bond and Solvent-Dependent Formation of Biradicals and Zwitterions" @default.
• W2024372298 cites W1480154856 @default.
• W2024372298 cites W1488191205 @default.
• W2024372298 cites W1588242064 @default.
• W2024372298 cites W1976948558 @default.
• W2024372298 cites W1977492358 @default.
• W2024372298 cites W1978208461 @default.
• W2024372298 cites W1981705281 @default.
• W2024372298 cites W1986027605 @default.
• W2024372298 cites W1991730965 @default.
• W2024372298 cites W1991828698 @default.
• W2024372298 cites W1994098122 @default.
• W2024372298 cites W1994291796 @default.
• W2024372298 cites W1995381324 @default.
• W2024372298 cites W1998290446 @default.
• W2024372298 cites W2001368228 @default.
• W2024372298 cites W2003133664 @default.
• W2024372298 cites W2004277125 @default.
• W2024372298 cites W2007231854 @default.
• W2024372298 cites W2016697752 @default.
• W2024372298 cites W2017302376 @default.
• W2024372298 cites W2020638377 @default.
• W2024372298 cites W2024655571 @default.
• W2024372298 cites W2025446864 @default.
• W2024372298 cites W2029569094 @default.
• W2024372298 cites W2033191396 @default.
• W2024372298 cites W2034468906 @default.
• W2024372298 cites W2038754172 @default.
• W2024372298 cites W2046085941 @default.
• W2024372298 cites W2047560793 @default.
• W2024372298 cites W2050676384 @default.
• W2024372298 cites W2052197848 @default.
• W2024372298 cites W2057190715 @default.
• W2024372298 cites W2059531536 @default.
• W2024372298 cites W2061872291 @default.
• W2024372298 cites W2066624154 @default.
• W2024372298 cites W2069706565 @default.
• W2024372298 cites W2075043213 @default.
• W2024372298 cites W2077607433 @default.
• W2024372298 cites W2077618569 @default.
• W2024372298 cites W2078630174 @default.
• W2024372298 cites W2086731924 @default.
• W2024372298 cites W2089015527 @default.
• W2024372298 cites W2101964918 @default.
• W2024372298 cites W2111106016 @default.
• W2024372298 cites W2123301121 @default.
• W2024372298 cites W2128257344 @default.
• W2024372298 cites W2133605740 @default.
• W2024372298 cites W2137474438 @default.
• W2024372298 cites W2157068046 @default.
• W2024372298 cites W2170693595 @default.
• W2024372298 cites W2319330470 @default.
• W2024372298 cites W2325204277 @default.
• W2024372298 cites W278040073 @default.
• W2024372298 cites W2949956313 @default.
• W2024372298 cites W2950863843 @default.
• W2024372298 cites W2951957857 @default.
• W2024372298 cites W3004765228 @default.
• W2024372298 cites W3137365194 @default.
• W2024372298 cites W4213449901 @default.
• W2024372298 cites W4229738735 @default.
• W2024372298 cites W4237162299 @default.
• W2024372298 doi "https://doi.org/10.1021/ic9707319" @default.
• W2024372298 hasPublicationYear "1998" @default.
• W2024372298 type Work @default.
• W2024372298 sameAs 2024372298 @default.
• W2024372298 citedByCount "35" @default.
• W2024372298 countsByYear W20243722982012 @default.
• W2024372298 countsByYear W20243722982013 @default.
• W2024372298 countsByYear W20243722982018 @default.
• W2024372298 countsByYear W20243722982019 @default.
• W2024372298 countsByYear W20243722982021 @default.
• W2024372298 crossrefType "journal-article" @default.
• W2024372298 hasAuthorship W2024372298A5014875669 @default.
• W2024372298 hasAuthorship W2024372298A5024617682 @default.
• W2024372298 hasAuthorship W2024372298A5042128219 @default.
• W2024372298 hasAuthorship W2024372298A5067584431 @default.
• W2024372298 hasAuthorship W2024372298A5076429234 @default.
• W2024372298 hasAuthorship W2024372298A5080879830 @default.
• W2024372298 hasConcept C119824511 @default.
• W2024372298 hasConcept C121332964 @default.
• W2024372298 hasConcept C155647269 @default.
• W2024372298 hasConcept C161790260 @default.
• W2024372298 hasConcept C171001562 @default.
• W2024372298 hasConcept C178790620 @default.
• W2024372298 hasConcept C185592680 @default.
• W2024372298 hasConcept C187961010 @default.
• W2024372298 hasConcept C2776303508 @default.

• next