2,7-Fluorenediyl-Bridged Complexes Containing Electroactive “Fe(η5‑C5Me5)(κ2‑dppe)CC–” End Groups: Molecular Wires and Remarkable Nonlinear Electrochromes

• Published in: Organometallics 2015-11, Vol.34 (22), p.5418-5437
• Main Authors: Malvolti, Floriane, Rouxel, Cédric, Triadon, Amédée, Grelaud, Guillaume, Richy, Nicolas, Mongin, Olivier, Blanchard-Desce, Mireille, Toupet, Loic, Razak, Fazira I. Abdul, Stranger, Robert, Samoc, Marek, Yang, Xinwei, Wang, Genmiao, Barlow, Adam, Cifuentes, Marie P, Humphrey, Mark G, Paul, Frédéric
• Format: Article
• Language: English
• Subjects: Chemical Sciences
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.5b00769

The 2,7-fluorenyl-bridged Fe­(η5-C5Me5)­(κ2-dppe)­[CC­(2,7-C13H6Bu2)­CC]­Fe­(η5-C5Me5)­(κ2-dppe) (1a), its extended analogue Fe­(η5-C5Me5)­(κ2-dppe)­[CC­(1,4-C6H4)­CC­(2,7-C13H6Bu2)­CC­(1,4-C6H4)­CC]­(η5-C5Me5)­(κ2-dppe)Fe (1b), and the corresponding mononuclear complexes Fe­(η5-C5Me5)­(κ2-dppe)­[CC­(2-C13H7Bu2)] (2a) and Fe­(η5-C5Me5)­(κ2-dppe)­[CC­(1,4-C6H4)­CC­(2-C13H7Bu2)] (2b), which model half of these molecules, have been synthesized and characterized in their various redox states. The molecular wire characteristics of the dinuclear complexes were examined in their mixed-valent states, with progression from 1a[PF6] to 1b[PF6] resulting in a sharp decrease in electronic coupling. The cubic nonlinear optical properties of these species were investigated over the visible and near-IR range, a particular emphasis being placed on their multiphoton absorption properties; the complexes are shown to function as redox-switchable nonlinear chromophores at selected wavelengths, and the more extended derivatives are shown to exhibit the more promising NLO performance.