Mixed-Valence Organics: A Window into Fundamental Electron-Transfer Processes

Mixed-valence compounds, in which two or more redox centers in different formal oxidation states are linked, can serve as valuable tools in the fundamental study of electron-transfer (ET) processes. Organic MV systems, in particular, have attracted increasing interest as the multitude of available synthetic procedures allows for one to control the electronic coupling over a large range. In some cases, these organic MV systems provide deeper insight into the behavior of organic electronic and optical materials. The inherent ET properties and patterns of charge (de)localization in MV systems strongly depend on the interplay and strengths of electronic and vibrational interactions [i.e., transfer integrals (electronic coupling) and intermolecular reorganization energies, respectively]. In this work we aim to provide a theoretical understanding of the electronic and vibrational interplay to provide further insight in both intramolecular and intermolecular ET processes.

Research highlights:
  • Intramolecular Electron-Transfer Rates In Mixed-Valence Triarylamines: Measurement By Variable-Temperature Esr Spectroscopy And Comparison With Optical Data, Lancaster, K; Odom, SA; Jones, SC; Thayumanavan, S; Marder, SR; Bredas, JL; Coropceanu, V; Barlow, S,Journal Of The American Chemical Society, 131, 1717-1723 [2009]
  • Trends In Electron-Vibration And Electronic Interactions In Bis(Dimethylamino) Mixed-Valence Systems: A Joint Experimental And Theoretical Investigation, Risko, C; Coropceanu, V; Barlow, S; Geskin, V; Schmidt, K; Gruhn, NE; Marder, SR; Bredas, JL, Journal Of Physical Chemistry C, 112, 7959-7967 [2008]
  • A New Class Of Mixed-Valence Systems With Orbitally Degenerate Organic Redox Centers. Examples Based On Hexa-Rhenium Molecular Prisms, Dinolfo, PH; Coropceanu, V; Bredas, JL; Hupp, JT, Journal Of The American Chemical Society, 128, 12592-12593 [2006]
  • Electronic Coupling In Tetraanisylarylenediamine Mixed-Valence Systems: The Interplay Between Bridge Energy And Geometric Factors, Lambert, C; Risko, C; Coropceanu, V; Schelter, J; Amthor, S; Gruhn, NE; Durivage, JC; Bredas, JL, Journal Of The American Chemical Society, 127, 8508-8516 [2005]
Recent papers on mixed-valency:
  • Bis [Bis-(4-Alkoxyphenyl) Amino] Derivatives Of Dithienylethene, Bithiophene, Dithienothiophene And Dithienopyrrole: Palladium-Catalysed Synthesis And Highly Delocalised Radical Cations, Odom, SA; Lancaster, K; Beverina, L; Lefler, KM; Thompson, NJ; Coropceanu, V; Bredas, JL; Marder, SR; Barlow, S, Chemistry-A European Journal, 13, 9637-9646 [2007]
  • The Impact Of Symmetric Modes On Intramolecular Electron Transfer: A Semi-Classical Approach, Coropceanu, V; Boldyrev, SI; Risko, C; Bredas, JL, Chemical Physics, 326, 107-114[2006]
  • Isolation And Crystal Structures Of Two Singlet Bis(Triarylamine) Dications With Nonquinoidal Geometries, Zheng, SJ; Barlow, S; Risko, C; Kinnibrugh, TL; Khrustalev, VN; Jones, SC; Antipin, MY; Tucker, NM; Timofeeva, TV; Coropceanu, V; Bredas, JL; Marder, SR,Journal Of The American Chemical Society, 128, 1812-1817 [2006]
  • Intervalence Transitions In The Mixed-Valence Monocations Of Bis(Triarylamines) Linked With Vinylene And Phenylene-Vinylene Bridges, Barlow, S; Risko, C; Chung, SJ; Tucker, NM; Coropceanu, V; Jones, SC; Levi, Z; Bredas, JL; Marder, SR, Journal Of The American Chemical Society, 127, 16900-16911 [2005]
  • Borderline Class II/III Ligand-Centered Mixed Valency In A Porphyrinic Molecular Rectangle, Dinolfo, PH; Lee, SJ; Coropceanu, V; Bredas, JL; Hupp, JT, Inorganic Chemistry,44, 5789-5797 [2005]
  • A Mixed-Valence Bis(Diarylamino) Stilbene: Crystal Structure And Comparison Of Electronic Coupling With Biphenyl And Tolane Analogues, Barlow, S; Risko, C; Coropceanu, V; Tucker, NM; Jones, SC; Levi, Z; Khrustalev, VN; Antipin, MY; Kinnibrugh, TL; Timofeeva, T; Marder, SR; Bredas, JL, Chemical Communications, , 764-766 [2005]