Transannular Effects in Dicobalta−Superphane Complexes on the Mixed-Valence Class II/Class III Interface:  Distinguishing between Spin and Charge Delocalization by Electrochemistry, Spectroscopy, and ab Initio Calculations

1999 ◽  
Vol 121 (40) ◽  
pp. 9343-9351 ◽  
Author(s):  
Michael E. Stoll ◽  
Sherri R. Lovelace ◽  
William E. Geiger ◽  
Holger Schimanke ◽  
Isabella Hyla-Kryspin ◽  
...  
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Mixed Valence ◽  
Class Ii ◽  
Class Iii ◽  
Charge Delocalization

Correction to From Molecular Wires to Molecular Resistors: TCNE, a Class-III/Class-II Mixed-Valence Chemical Switch

2014 ◽  
Vol 33 (19) ◽  
pp. 5618-5618 ◽  
Author(s):  
Alexandre Burgun ◽  
Benjamin G. Ellis ◽  
Thierry Roisnel ◽  
Brian W. Skelton ◽  
Michael I. Bruce ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Molecular Wires ◽  
Class Ii ◽  
Class Iii

Infrared Study of the Class II/Class III Boundary in Mixed-Valence Dinuclear Ruthenium Complexes

2001 ◽  
Vol 123 (7) ◽  
pp. 1396-1402 ◽  
Author(s):  
Maria C. DeRosa ◽  
Christopher A. White ◽  
Christopher E. B. Evans ◽  
Robert J. Crutchley
Keyword(s):  
Mixed Valence ◽  
Ruthenium Complexes ◽  
Class Ii ◽  
Class Iii ◽  
Infrared Study ◽  
Dinuclear Ruthenium ◽  
Dinuclear Ruthenium Complexes

Pseudo-para-dinitro[2.2]paracyclophane Radical Anion, a Mixed-Valence System Poised on the Class II/Class III Borderline

2005 ◽  
Vol 127 (3) ◽  
pp. 920-925 ◽  
Author(s):  
Stephen F. Nelsen ◽  
Asgeir E. Konradsson ◽  
João P. Telo
Keyword(s):  
Radical Anion ◽  
Mixed Valence ◽  
Class Ii ◽  
Class Iii

Resonance Raman spectroscopic study of solvent-dependent coexistence of localized and delocalized dinitroaromatic radical anions

2014 ◽  
Vol 92 (10) ◽  
pp. 940-947 ◽  
Author(s):  
Ryan M. Hoekstra ◽  
Yen-Ting Chen ◽  
Matthew D. Kiesz ◽  
João P. Telo ◽  
Rachel M. Stephenson ◽  
...  
Keyword(s):  
Broad Band ◽  
Mixed Valence ◽  
Resonance Raman ◽  
Reorganization Energy ◽  
Class Ii ◽  
Radical Anions ◽  
Class Iii ◽  
Excitation Energies ◽  
Absorption Region ◽  
Stretch Mode

Optical absorption spectra of three dinitroaromatic radical anions, 2,7-dinitro-9,9-dimethylfluorene (1•−), 4,4′-dinitrobiphenyl (2•−), and 4,4′-dinitrotolane (3•−) in solvents THF, HMPA, and MeCN show both an unresolved broad band characteristic of charge-localized mixed valence species (Robin-Day classification Class II), and a vibronically structured band of the delocalized species (Class III). With decreasing solvent reorganization energy, a greater portion of the compounds become charge-delocalized. In particular, 1•− with the greatest coupling, is almost entirely composed of the delocalized species in all solvents. An intense Raman mode is used to identify the charge-bearing unit as the nitrobenzene moiety. Resonance Raman profiles are utilized to gain detailed information of vibrational modes. The out-of-phase ring lengthening stretch mode is observed to be enhanced at higher excitation energies, corresponding to the absorption band of the Class II species, while the in-phase ring lengthening stretch mode, a totally symmetric vibration, is most strongly enhanced in the absorption region of the Class III species. Resonance Raman profiles support the solvent-dependent coexistence of Class II and Class III molecules of the same chemical composition.

Optically probing the localized to delocalized transition in Mo2–Mo2 mixed-valence systems

2017 ◽  
Vol 53 (21) ◽  
pp. 3030-3033 ◽  
Author(s):  
Yi Yang Wu ◽  
Miao Meng ◽  
Gang Yi Wang ◽  
Pengju Feng ◽  
Chun Y. Liu
Keyword(s):  
Charge Transfer ◽  
Absorption Band ◽  
Energy Intensity ◽  
Mixed Valence ◽  
Class Ii ◽  
Class Iii ◽  
Spectral Parameters ◽  
Band Energy ◽  
Charge Transfer Absorption Band ◽  
Intervalence Charge Transfer

A transition of mixed-valence systems from Class II to Class III crossing the Class II–III borderline is achieved by four thienylene-bridged Mo2 dimers, and is probed using spectral parameters of intervalence charge transfer absorption (band energy, intensity and shape). This study offers fresh and detailed observations of optical behaviors of MV compounds in different regimes.

From Molecular Wires to Molecular Resistors: TCNE, a Class-III/Class-II Mixed-Valence Chemical Switch

2014 ◽  
Vol 33 (16) ◽  
pp. 4209-4219 ◽  
Author(s):  
Alexandre Burgun ◽  
Benjamin G. Ellis ◽  
Thierry Roisnel ◽  
Brian W. Skelton ◽  
Michael I. Bruce ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Molecular Wires ◽  
Class Ii ◽  
Class Iii

Contrasting electroabsorbance behavior of two borderline class II/class III mixed-valence systems

2005 ◽  
Vol 319 (1-3) ◽  
pp. 28-38 ◽  
Author(s):  
Peter H. Dinolfo ◽  
Robert D. Williams ◽  
Joseph T. Hupp
Keyword(s):  
Mixed Valence ◽  
Class Ii ◽  
Class Iii
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