Charge and Spin Confinement to the Amine Site in 3-Connected Triarylamine Vinyl Ruthenium Conjugates

Polit, Walther; Mücke, Philipp; Wuttke, Evelyn; Exner, Thomas E.; Winter, Rainer F.

doi:10.1021/om4007455

Cited by 35 publications

(36 citation statements)

References 96 publications

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“…1,43,44 That assignment agrees well with the observed shift to lower energy as the 4-substituent at the styryl ligand becomes more electron releasing, whereby the liganddominated HOMO is more destabilized than the Ru-based LUMO. A much more intense absorption corresponding to the HOMO → LUMO+1 excitation is observed in the near-UV region.…”

Section: ■ Introductionsupporting

confidence: 82%

“…The synthesis and physical characterization of the five-coordinated precursor 1c have been described previously. 43 General Procedure for the Synthesis of the 5-Coordinated Complexes [Ru(CO)Cl(P i Pr 3 ) 2 (CHCH-4-C 6 H 4 -X). To a stirred solution of HRu(CO)Cl(P i Pr 3 ) 2 (75.3 mg, 0.15 mmol, 1 equiv) in 10 mL of CH 2 Cl 2 , was slowly added a solution of the respective para-substituted phenylacetylene (0.17 mmol, 1.1 equiv) in 10 mL of CH 2 Cl 2 .…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Figures S113−S125 of the Supporting Information contain graphical representations of the results for the other complexes. Band assignments were aided by TD-DFT calculations on the model complexes 1 Me -H′ 0/+ with the unsubstituted styryl ligand 43 and complex 2b′ 0/+ ; the corresponding results are provided in Table 6.…”

Section: ■ Introductionmentioning

confidence: 99%

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Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

et al. 2015

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A series of ruthenium styryl complexes with potentially noninnocent κ 2 [N,O] − or κ 2 [N,S] − ligands have been prepared by treatment of 5-coordinated 16-valence-electron ruthenium styryl complexes Ru(CO)Cl(P i Pr 3 ) 2 (CHCH-C 6 H 4 -4R) with deprotonated bidentate 2-hydroxy-or 2-mercaptopyridines or 2-hydroxy-or 2-mercaptoquinolines. These 6-coordinated complexes have been characterized by NMR and IR spectroscopy and by cyclic voltammetry. Moreover, the structures of complexes 1d, 2a, 3c, 5b, and 6b have been established by X-ray crystallography. Our results indicate that the pyridine-derived complexes exist as two isomers that differ with respect to the orientation of the κ 2 [N,O] − or κ 2 [N,S] − donor ligands relative to the CO and alkenyl ligands in the equatorial plane. The equilibrium between the two isomers is thermodynamically controlled. Thus, the relative amount of the minor isomer increases at higher temperatures. With the 2-hydroxyquinoline-or 2-mercaptoquinoline-derived ligands only one isomer is observed. Electrochemical studies show that these complexes undergo one or two reversible consecutive one-electron oxidations, the potentials of which respond to the electronic properties of the 4-substituent at the styryl ligand and those of the ancillary chelate ligand. Strong ligand contributions to the first oxidation of the complexes were experimentally verified by IR and EPR spectroelectrochemistry. Quantum chemical calculations reproduce our experimental results, including the positions of the Ru(CO) vibrational bands of the neutral complexes and of their corresponding radical cations. Our combined results indicate that the oxidation of all complexes is dominated by the styryl ligand, irrespective of the electronic nature of the 4-substituent and of the [N,O] − or [N,S] − chelate ligand.

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Section: ■ Introductionsupporting

confidence: 82%

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

et al. 2015

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“…3, the crystallographic analysis suggests typical propeller-like arrangements for the three aromatic rings around each nitrogen center with respect to the triarylamine termini. The bond parameters including the C—C and C—N distances and the C—N—C angles, fall in the normal range of the data reported in similar systems4344. In addition, a good coincidence between these data and the corresponding computed values can also be found in the later content.…”

Section: Resultssupporting

confidence: 78%

Elaborately Tuning Intramolecular Electron Transfer Through Varying Oligoacene Linkers in the Bis(diarylamino) Systems

Zhang

Zhao

Yang

et al. 2016

Sci Rep

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The research efforts on oligoacene systems are still relatively limited mainly due to the synthetic challenge and the extreme instability of longer acenes. Herein, these two issues have been overcome through elaborative modification and the stable pentacene species has been successfully synthesized. Additionally, a series of bis(diarylamino) compounds linked by variable-length oligoacene bridges ranging from one to five fused rings (benzene (1a), naphthalene (1b), anthracene (1c), tetracene (1d) and pentacene (1e)) have been prepared to probe the effect of the extent of π-conjugation on the electron transfer properties. Compound 1c exhibits a high planarity between the anthracyl bridge and the two nitrogen cores and the molecular packing shows a two-dimensional herringbone characteristic. Combined studies based on electrochemistry and spectroelectrochemistry demonstrate that (i) the electronic coupling across the oligoacene linkers between two diarylamine termini exponentially decrease with a moderate attenuation constant (β) of 0.14 Å−1 in these length-modulated systems and (ii) the associated radical cations [1a]+–[1e]+ are classified as the class II Robin–Day mixed-valence systems. Furthermore, density functional theory (DFT) calculations have been conducted to gain insight into the nature of electron transfer processes in these oligoacene systems.

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“…The other metrical data are unremarkable compared to those of closely related structures of five‐, , , , and six‐coordinate[3a], alkenylruthenium complexes with the Ru(CO)(P i Pr 3 ) 2 (L) moiety and warrant no further discussion. Owing to the strong σ‐ trans influence of the alkenyl ligand, the Ru–O bond opposite the latter ligand is longer than that opposite the carbonyl ligand by ca.…”

Section: Resultsmentioning

confidence: 88%

Oxidized Styrylruthenium–Ferrocene Conjugates: From Valence Localization to Valence Tautomerism

et al. 2016

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Abstract:We report on ferrocenyl-styrylruthenium conjugates Fc-C 6 H 4 -CH=CH-Ru(CO)(PiPr 3 ) 2 (L) in which the electron density at the alkenylruthenium site is modified by the variation of the coligand L [L = Cl, acetylacetonate (acac), hexafluoroacetylacetonate (hfac), or dipivaloylmethane (dpvm); Fc = ferrocenyl]. Crystallographic studies on three derivatives provide snapshots of the conformational degrees of freedom for rotation around the vinyl-phenylene and phenylene-ferrocenyl linkages. All four complexes undergo two consecutive, reversible one-electron oxidations, the potentials of which depend on the ligand L. On the basis of IR spectroelectrochemistry results, the first oxidations of the less electron-rich chlorido and hfac complexes are biased strongly towards the ferrocenyl site. However, the radical cation of the acac complex exists as two equilibrating

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Charge and Spin Confinement to the Amine Site in 3-Connected Triarylamine Vinyl Ruthenium Conjugates

Cited by 35 publications

References 96 publications

Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

Elaborately Tuning Intramolecular Electron Transfer Through Varying Oligoacene Linkers in the Bis(diarylamino) Systems

Oxidized Styrylruthenium–Ferrocene Conjugates: From Valence Localization to Valence Tautomerism

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