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Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

AutorCoe, Benjamin J.; Helliwell, Madeleine; Brunschwig, Bruce S.; Clays, Koen; Garín, Javier; Orduna, Jesús
Palabras claveDensity functional calculations
Nonlinear optics
Ferrocenyl derivatives
Coordination compounds
Fecha de publicación2013
CitaciónChemistry - A European Journal 19(21): 6613-6629 (2013)
ResumenNew complexes with six ferrocenyl (Fc) groups connected to ZnII or CdII tris(2,2′-bipyridyl) cores are described. A thorough characterisation of their BPh4− salts includes two single-crystal X-ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(FeII)-π* metal-to-ligand charge-transfer (MLCT) bands accompany the π-π* intraligand charge-transfer absorptions in the near UV region. Each complex shows a single, fully reversible FeIII/II wave when probed electrochemically. Molecular quadratic nonlinear optical (NLO) responses are determined by using hyper-Rayleigh scattering and Stark spectroscopy. The latter gives static first hyperpolarisabilities β0 reaching as high as approximately 10−27 esu and generally increasing with π-conjugation extension. Z-scan cubic NLO measurements reveal high two-photon absorption cross-sections σ2 of up to 5400 GM in one case. DFT calculations reproduce the π-conjugation dependence of β0, and TD-DFT predicts three transitions close in energy contributing to the MLCT bands. The lowest energy transition has octupolar character, whereas the other two are degenerate and dipolar in nature
Identificadoresdoi: 10.1002/chem.201204453
issn: 0947-6539
e-issn: 1521-3765
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