Evidence for specific solvent-solute interactions as a major contributor to the Franck-Condon energy in intervalence-transfer absorptions of ruthenium ammine complexes

Chang, Junghae P.; Fung, Ella Y.; Curtis, James A.

doi:10.1021/ic00243a034

Cited by 99 publications

(99 citation statements)

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“…However, for complexes 3A C H T U N G T R E N N U N G (PF 6 ) and 4- (Figure 2), albeit with shallow slopes. Previous studies by the groups of Curtis, [22] Denning, [24] and Kwan [25] all reported an ascending order of DE 1/2 with increasing solvent donicity. The complexes studied all contained a {MA C H T U N G T R E N N U N G (NH 3 ) n } moiety, in which specific NH 3 -solvent hydrogen-bonding interactions were thought to play a decisive role.…”

Section: Synthesismentioning

confidence: 87%

“…[22] They found a linear relationship between the electrochemical potential difference, DE 1/2 , of two redox sites and the Gutmann donor number [23] (DN) within the same compound series. In addition, the relationships for E op versus DE 1/2 and (E op ÀDE 1/2 ) versus DN were also linear.…”

Section: Abstract: Four Heterodimetallic Complexes [Rua C H T U N G Tmentioning

confidence: 99%

“…[22] On the basis of Equations (1)- (3), if l i and l 0 remain constant for a given series compounds in the same solvent,…”

Section: H T U N G T R E N N U N G (Pf 6 ) For Complexes 3a C H T U mentioning

confidence: 99%

“…Such a relationship has indeed been documented in some asymmetric MV systems. [22,25] However, if l i and/or l 0 change as…”

Section: H T U N G T R E N N U N G (Pf 6 ) For Complexes 3a C H T U mentioning

confidence: 99%

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Substituent and Solvent Effects on the Electrochemical Properties and Intervalence Transfer in Asymmetric Mixed‐Valent Complexes Consisting of Cyclometalated Ruthenium and Ferrocene

Shao

Kang

et al. 2013

Chemistry An Asian Journal

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Four heterodimetallic complexes [Ru(Fcdpb)(L)](PF6) (Fcdpb=2-deprotonated form of 1,3-di(2-pyridyl)-5-ferrocenylbenzene; L=2,6-bis-(N-methylbenzimidazolyl)-pyridine (Mebip), 2,2':6',2''-terpyridine (tpy), 4-nitro-2,2':6',2''-terpyridine (NO2tpy), and trimethyl-4,4',4''-tricarboxylate-2,2':6',2''-terpyridine (Me3tctpy)) have been prepared. The electrochemical and spectroelectrochemical properties of these complexes have been examined in CH2Cl2, CH3NO2, CH3CN, and acetone. These complexes display two consecutive redox couples owing to the stepwise oxidation of the ferrocene (Fc) and ruthenium units, respectively. The potential difference, ΔE(1/2)(E(1/2)(Ru(II/III))-E(1/2)(Fc(0/+))), decreased slightly with increasing solvent donocity. The mixed-valent states of these complexes have been generated by electrolysis and the resulting intervalence charge-transfer (IVCT) bands have been analyzed by Hush theory. Good linear relationships exist between the energy of the IVCT band, E(op), and ΔE(1/2) of four mixed-valent complexes in a given solvent.

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Section: Synthesismentioning

confidence: 87%

Section: Abstract: Four Heterodimetallic Complexes [Rua C H T U N G Tmentioning

confidence: 99%

“…[22] On the basis of Equations (1)- (3), if l i and l 0 remain constant for a given series compounds in the same solvent,…”

Section: H T U N G T R E N N U N G (Pf 6 ) For Complexes 3a C H T U mentioning

confidence: 99%

“…Such a relationship has indeed been documented in some asymmetric MV systems. [22,25] However, if l i and/or l 0 change as…”

Section: H T U N G T R E N N U N G (Pf 6 ) For Complexes 3a C H T U mentioning

confidence: 99%

See 2 more Smart Citations

Substituent and Solvent Effects on the Electrochemical Properties and Intervalence Transfer in Asymmetric Mixed‐Valent Complexes Consisting of Cyclometalated Ruthenium and Ferrocene

Shao

Kang

et al. 2013

Chemistry An Asian Journal

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“…Variations in the position, intensity, and shape of the absorption spectra can be direct measures of solute and solvent molecule interactions [40]. Due to the Frank-Condon principle, the excited state solvent shell is not in equilibrium with the excited state molecule, i.e., the solute [41].…”

Section: Uv-visible Spectrophotometry Characterization: a Study Of Somentioning

confidence: 99%

A Combined XRD, Solvatochromic, and Cyclic Voltammetric Study of Poly (3,4-Ethylenedioxythiophene) Doped with Sulfonated Polyarylethersulfones: Towards New Conducting Polymers

et al. 2018

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Despite the poor solubility in organic solvents, poly (3,4-ethylenedioxythiophene) (PEDOT) is one of the most successful conducting polymers. To improve PEDOT conductivity, the dopants commonly used are molecules/polymers carrying sulfonic functionalities. In addition to these species, sulfonated polyarylethersulfone (SPAES), obtained via homogeneous synthesis with different degrees of sulfonation (DS), can be used thanks to both the tight control over the DS and the charge separation present in SPAES structure. Here, PEDOTs having enhanced solubility in the chosen reaction solvents (N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone) were synthesized via a high-concentration solvent-based emulsion polymerization with very low amounts of SPAES as dopant (1% w/w with respect to EDOT monomer), characterized by different DS. The influence of solvents and of the adopted doping agent was studied on PEDOT_SPAESs analyzing (i) the chemical structure, comparing via X-ray diffraction (XRD) the crystalline structures of undoped and commercial PEDOTs with PEDOT_SPAES' amorphous structure; (ii) solvatochromic behavior, observing UV absorption wavelength variation as solvents and SPAES' DS change; and (iii) electrochemical properties: voltammetric peak heights of PEDOT_SPAES cast onto glassy carbon electrodes differ for each solvent and in general are better than the ones obtained for neat SPAES, PEDOTs, and glassy carbon.

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Electrochemistry of Copper

Rorabacher

Schroeder

2006

Encyclopedia of Electrochemistry

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The sections in this article are Introduction Oxidation States of Copper Reference Standards for Potential Values in Nonaqueous Solvent Studies Methods Used for Potential Measurements Potentials Involving Solvated Copper Species Electrochemical Considerations for Copper( II / I ) Complexes Involving Multidentate Ligands Trends in Potentials of Copper( II / I ) Complexes with Multidentate Ligands Dependence of Copper( II / I ) Potentials on Ligand Properties Correlation of Potentials to Copper( II ) Complex Stability Constants Mechanistic Aspects of Copper( II / I ) Electron Transfer Ligand Conformational Change Complex Dissociation/Formation Interconversion of Ternary and Binary Complexes Interconversion of 1:2 and 1:1 Complexes Dimeric/Monomeric Species Other Phenomena Affecting Electrochemical Behavior Ligand Oxidation or Reduction Electroplating of Copper Biological Copper Systems Other Copper( II / I ) Systems Unidentate Ligand Complexes Hydroxide Complexes Halide Complexes Cyanide and Thiocyanate Complexes Ammonia Complexes Complexes with Acetate and Other Common Brønsted Bases Noncomplexing Buffer Systems Binuclear Complexes Copper( III / II ) Systems

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Evidence for specific solvent-solute interactions as a major contributor to the Franck-Condon energy in intervalence-transfer absorptions of ruthenium ammine complexes

Cited by 99 publications

References 1 publication

Substituent and Solvent Effects on the Electrochemical Properties and Intervalence Transfer in Asymmetric Mixed‐Valent Complexes Consisting of Cyclometalated Ruthenium and Ferrocene

Substituent and Solvent Effects on the Electrochemical Properties and Intervalence Transfer in Asymmetric Mixed‐Valent Complexes Consisting of Cyclometalated Ruthenium and Ferrocene

A Combined XRD, Solvatochromic, and Cyclic Voltammetric Study of Poly (3,4-Ethylenedioxythiophene) Doped with Sulfonated Polyarylethersulfones: Towards New Conducting Polymers

Electrochemistry of Copper

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