“…Expanding these investigations to more complicated ligands and metal complexes and even bimetallic complexes, yielded similar good results [25]. This eventually led to the MLCT complexes of group‐8 in the transition metal series, namely iron [26], ruthenium [27] and now also the osmium‐polypyridine complexes [Os(X) 3 ] 2+ , where X=5‐chloro‐1,10‐phenanthroline ( 1 ), 2,2’‐bipyridine ( 2 ), 1,10‐phenanthroline ( 3 ), 4‐methyl‐1,10‐phenanthroline ( 4 ), 4,4’‐di‐tert‐butyl‐2,2’‐bipyridine ( 5 ), 4,4’‐dimethyl‐2,2’‐bipyridine ( 6 ), 3,4,7,8‐tetramethyl‐1,10‐phenanthroline ( 7 ) and 4,4’‐dimethoxy‐2,2’‐bipyridine ( 8 ), as well as [Fe(X) 3 ] 2+ with X=4,4’‐di‐tert‐butyl‐2,2’‐bipyridine ( 9 ), as listed in Table 1 below.…”
Osmium(II) polypyridyl complexes may be useful in H 2 O and CO 2 photo-catalytic reduction and dyesensitized solar cell research. Altering substituents on the polypyridyl ligands allows for spectral and electronic tuning of the osmium(II) polypyridyl complexes. The cyclic voltammograms and UV-visible spectra of a series of electronically altered bipyridine and phenanthroline osmium(II) complexes are presented. Os II/III experimental oxidation potentials correlate linearly (R 2 = 0.99) with density functional theory (DFT) implicit solvent model computed ionization potentials and highest occupied molecular orbital (HOMO) energies. The hereby obtained linear relationship provides a theoretical computational tool that may be used for the predetermination of redox potentials of related osmium(II) polypyridyl complexes. Comparison between similar correlations for elements in the same group, namely Fe, Ru and Os, revealed remarkably similar patterns. Of the three, Os II bipyridyl is most readily oxidized (0.452 V), followed by Fe II (0.682 V) and then Ru II (0.883 V). Spectra of the Os II complexes where λ max values range from 392 to 442 nm, were closely simulated by time-dependant DFT computed electronic oscillators. Osmium(II) polypyridyl complex absorbances span almost the entire visible spectrum.
“…Expanding these investigations to more complicated ligands and metal complexes and even bimetallic complexes, yielded similar good results [25]. This eventually led to the MLCT complexes of group‐8 in the transition metal series, namely iron [26], ruthenium [27] and now also the osmium‐polypyridine complexes [Os(X) 3 ] 2+ , where X=5‐chloro‐1,10‐phenanthroline ( 1 ), 2,2’‐bipyridine ( 2 ), 1,10‐phenanthroline ( 3 ), 4‐methyl‐1,10‐phenanthroline ( 4 ), 4,4’‐di‐tert‐butyl‐2,2’‐bipyridine ( 5 ), 4,4’‐dimethyl‐2,2’‐bipyridine ( 6 ), 3,4,7,8‐tetramethyl‐1,10‐phenanthroline ( 7 ) and 4,4’‐dimethoxy‐2,2’‐bipyridine ( 8 ), as well as [Fe(X) 3 ] 2+ with X=4,4’‐di‐tert‐butyl‐2,2’‐bipyridine ( 9 ), as listed in Table 1 below.…”
Osmium(II) polypyridyl complexes may be useful in H 2 O and CO 2 photo-catalytic reduction and dyesensitized solar cell research. Altering substituents on the polypyridyl ligands allows for spectral and electronic tuning of the osmium(II) polypyridyl complexes. The cyclic voltammograms and UV-visible spectra of a series of electronically altered bipyridine and phenanthroline osmium(II) complexes are presented. Os II/III experimental oxidation potentials correlate linearly (R 2 = 0.99) with density functional theory (DFT) implicit solvent model computed ionization potentials and highest occupied molecular orbital (HOMO) energies. The hereby obtained linear relationship provides a theoretical computational tool that may be used for the predetermination of redox potentials of related osmium(II) polypyridyl complexes. Comparison between similar correlations for elements in the same group, namely Fe, Ru and Os, revealed remarkably similar patterns. Of the three, Os II bipyridyl is most readily oxidized (0.452 V), followed by Fe II (0.682 V) and then Ru II (0.883 V). Spectra of the Os II complexes where λ max values range from 392 to 442 nm, were closely simulated by time-dependant DFT computed electronic oscillators. Osmium(II) polypyridyl complex absorbances span almost the entire visible spectrum.
“…1 for the series of complexes of this data study. Presented data is related to the research article “Electrochemistry and spectroscopy of substituted [Ru(phen) 3 ] 2+ and [Ru(bpy) 3 ] 2+ complexes” [1]. Redox data of these Ru(II) complexes are important for application as redox indicators, catalysts and photo-active mediators in dye-sensitized solar cells (DSSC) [3,4].…”
Section: Datamentioning
confidence: 99%
“…14, 0.10 Vs −1 scans from Ref. [1]), are tabulated in Table 1, Table 2, Table 3, Table 4, Table 5, Table 6, Table 7, Table 8, Table 9, Table 10, Table 11, Table 12, Table 13.Fig. 1Structure and complex numbering of the polypyridine complexes of Ru(II).Fig.…”
Section: Datamentioning
confidence: 99%
“…The data here-in presented is associated to the research article, Electrochemistry and spectroscopy of substituted [Ru(phen) 3 ] 2+ and [Ru(bpy)3] 2+ complexes [1]. Redox data obtained from cyclic voltammetry experiments of the oxidation of Ru(II) to Ru(III) of thirteen Ru(II)-polypyridine complexes is presented in this data in brief article.…”
mentioning
confidence: 99%
“…The data here-in presented is associated to the research article, Electrochemistry and spectroscopy of substituted [Ru(phen) 3 ] 2+ and [Ru(bpy)3] 2+ complexes [1].…”
The data here-in presented is associated to the research article, Electrochemistry and spectroscopy of substituted [Ru(phen)3]2+ and [Ru(bpy)3]2+ complexes [1].Redox data obtained from cyclic voltammetry experiments of the oxidation of Ru(II) to Ru(III) of thirteen Ru(II)-polypyridine complexes is presented in this data in brief article. Data is obtained from the cyclic voltammograms at scan rates of two orders of magnitude (0.05–5.00 Vs−1) under similar experimental conditions, namely in acetonitrile as solvent and tetrabutylammonium hexafluorophosphate as supporting electrolyte, and reported versus the redox couple of Fe(II) of ferrocene.
Silica matrices hosting transition metal guest complexes may offer remarkable platforms for the development of advanced functional devices. We report here the elaboration of ordered and vertically oriented mesoporous silica thin films containing covalently attached tris(bipyridine)iron derivatives using a combination of electrochemically assisted self-assembly (EASA) method and Huisgen cycloaddition reaction. Such a versatile approach is primarily used to bind nitrogen-based chelating ligands such as (4-[(2-propyn-1-yloxy)]4'-methyl-2,2'-bypiridine, bpy') inside the nanochannels. Further derivatization of the bpy'-functionalized silica thin films is then achieved via a subsequent in-situ complexation step to generate [Fe-(bpy) 2 (bpy')] 2 + inside the mesopore channels. After giving spectroscopic evidences for the presence of such complexes in the functionalized film, electrochemistry is used to transformin a reversible way, while blue light irradiation (λ = 470 nm) enables populating the short-lived paramagnetic (S = 2)[Fe(bpy) 2 (bpy')] 2 + -functionalized ordered films are therefore both electro-and photoactive through the manipulation of the oxidation state and spin state of the confined complexes, paving the way for their integration in optoelectronic devices.
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