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Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Coe, Benjamin J. and Foxon, Simon P. and Helliwell, Madeleine and Rusanova, Daniela and Brunschwig, Bruce S. and Clays, Koen and Depotter, Griet and Nyk, Marcin and Samoc, Marek and Wawrzynek, Dominika and Garín, Javier and Orduna, Jesús (2013) Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents. Chemistry: a European Journal, 19 (21). pp. 6613-6629. ISSN 0947-6539. doi:10.1002/chem.201204453.

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New complexes with six ferrocenyl (Fc) groups connected to ZnII or Cd^(II) tris(2,2′-bipyridyl) cores are described. A thorough characterisation of their BPh_(4)− salts includes two single-crystal X-ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(Fe^(II))→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 Fe^(III/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 β_0 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 β_0, 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.

Item Type:Article
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Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: December 13, 2012; Published online: March 27, 2013. We thank the EPSRC for support (grants EP/D070732 and EP/G02099) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2011/03), The Foundation for Polish Science (Welcome grant to M.S.), MCyT-FEDER (CTQ2005–01368, CTQ2008–02942) and Gobierno de Aragon-Fondo Social Europeo (E39). B.S.B. acknowledges the Beckman Institute of the California Institute of Technology for support. We are grateful to Dr John E. Warren (Synchrotron Radiation Source, CCLRC, Daresbury Laboratory, Warrington, WA4 4AD, U.K.) for help with the data collection for the crystal structure determination of 1·6MeNO_2. We also thank Dr John Fielden (Manchester) and Dr Inge Asselberghs (Leuven) for carrying out preliminary HRS measurements, and Nick Van Steerteghem (Leuven) for assistance with these experiments. D.R. thanks Prof Robert Dryfe (Manchester) for helpful discussions about electrochemistry.
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/D070732
Engineering and Physical Sciences Research Council (EPSRC)EP/G02099
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)G.0312.08
University of LeuvenGOA/2011/03
Foundation for Polish ScienceUNSPECIFIED
Ciencia y Tecnologia (MCyT)CTQ2005–01368
Ciencia y Tecnologia (MCyT)CTQ2008–02942
Gobierno de Aragon-Fondo Social EuropeoE39
Caltech Beckman InstituteUNSPECIFIED
Fondo Europeo de Desarrollo Regional (FEDER)UNSPECIFIED
Subject Keywords:chromophores; coordination compounds; density functional calculations; ferrocenyl derivatives; nonlinear optics
Issue or Number:21
Record Number:CaltechAUTHORS:20130703-100044779
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Official Citation:Coe, B. J., Foxon, S. P., Helliwell, M., Rusanova, D., Brunschwig, B. S., Clays, K., Depotter, G., Nyk, M., Samoc, M., Wawrzynczyk, D., Garín, J. and Orduna, J. (2013), Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents. Chem. Eur. J., 19: 6613–6629. doi: 10.1002/chem.201204453
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:39203
Deposited On:03 Jul 2013 18:43
Last Modified:09 Nov 2021 23:43

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