Charge-Transfer Salts of 6,6-Dicyanopentafulvenes: From Topology to Charge Separation in Solution

Autor: Sophie Haberland, Georg Gescheidt, Daria Confortin, Michal Zalibera, François Diederich, Aaron D. Finke, Anne-Marie Kelterer, Christian Mensing
Rok vydání: 2018
Předmět:
Zdroj: Chemistry - A European Journal. 24:13616-13623
ISSN: 0947-6539
DOI: 10.1002/chem.201802486
Popis: 6,6-Dicyanopentafulvene derivatives and metallocenes with redox potentials appropriate for forming their radical anions form highly persistent donor-acceptor salts. The charge-transfer salts of 2,3,4,5-tetraphenyl-6,6-dicyanofulvene with cobaltocene (1⋅Cp2 Co) and 2,3,4,5-tetrakis(triisopropylsilyl)-6,6-dicyanofulvene with decamethylferrocene (2⋅Fc*) have been prepared. The X-ray structures of the two salts, formed as black plates, were obtained and are discussed herein. Compared with neutral dicyanopentafulvenes, the chromophores in the metallocene salts show substantial changes in bond lengths and torsional angles in the solid state. EPR, NMR, and optical spectroscopy, as well as superconducting quantum interference device (SQUID) measurements, reveal that charge-separation in the crystalline states and in frozen and fluid solutions depends on subtle differences of redox potentials, geometry, and on ion pairing. Whereas 1⋅Cp2 Co reveals paramagnetic character in the crystalline state and in solution, compound 2⋅Fc* shows a delicate balance between para- and diamagnetism, depending on the temperature and solvent characteristics.
Databáze: OpenAIRE
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