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Nonlinear Optical Chromophores with Two Ferrocenyl, Octamethylferrocenyl, or 4‑(Diphenylamino)phenyl Groups Attached to Rhenium(I) or Zinc(II) Centers

Coe, Benjamin J. and Foxon, Simon P. and Pilkington, Rachel A. and Sánchez, Sergio and Whittaker, Daniel and Clays, Koen and Depotter, Griet and Brunschwig, Bruce S. (2015) Nonlinear Optical Chromophores with Two Ferrocenyl, Octamethylferrocenyl, or 4‑(Diphenylamino)phenyl Groups Attached to Rhenium(I) or Zinc(II) Centers. Organometallics, 34 (9). pp. 1701-1715. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20150615-115928582

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Abstract

The compounds 4,4′-bis[(E)-2-R-vinyl]-2,2′-bipyridyl {R = ferrocenyl [(Fcv)_2bpy], octamethylferrocenyl [(Me_8Fcv)_2bpy] or 4-(diphenylamino)phenyl [(Dapv)_2bpy]} are used to prepare eight new complexes with Zn^(II)Cl_2, Zn^(II)(OAc)_2, or fac-Re^ICl(CO)_3 centers. The recently reported complex fac-Re^ICl(CO)_3[(Dapv)_2bpy] (Horvath, R. et al. Inorg. Chem. 2013, 52, 1304) is also studied. Electronic absorption spectra show intense d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) absorption bands, the relative energies of which correlate logically with the molecular structure. Cyclic voltammetry reveals a reversible oxidation wave for the Fc/Me_8Fc complexes, accompanied by quasireversible or irreversible ligand-based reductions. The Re complexes also show irreversible Re^(II/I) waves. Single-crystal X-ray structures are reported for (Me_8Fcv)_2bpy, Zn^(II)Cl_2[(Me_8Fcv)_2bpy], Zn^(II)(OAc)_2[(Fcv)_2bpy]·CHCl_3, and fac-Re^ICl(CO)_3[(Me_8Fcv)_2bpy]·0.5CHCl_3. Molecular first hyperpolarizabilities β are measured in DCM solutions via the hyper-Rayleigh scattering (HRS) technique at 1300 nm. Stark (electroabsorption) spectroscopic studies on only the MLCT bands in frozen butyronitrile allow the indirect estimation of lower limits for the overall static first hyperpolarizabilities β_0. Time-dependent density functional theory (TD-DFT) calculations on selected complexes confirm the expected assignments of their low energy absorption bands, with the best results obtained by using the M06 functional and Def2-TZVP/SVP/TZVPP mixed basis set. DFT predicts that the total static first hyperpolarizability β_(tot) increases in the Zn^(II)Cl_2 series in the order R = Fc < Me_8Fc < Dap, consistent with the HRS and Stark data. The computed β values increase substantially on moving from the gas phase to a DCM or MeCN solvent medium, and the essentially 2D nature of the chromophores leads to dominant β_(xxy) tensor components.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.organomet.5b00193DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00193PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.organomet.5b00193PublisherSupporting Information
ORCID:
AuthorORCID
Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Received: March 9, 2015. Published: April 30, 2015. We thank the EPSRC for support (a Ph.D. studentship for R.A.P. and grants EP/J018635/1 and EP/K039547/1) and acknowledge financial support from the Hercules Foundation, the Fund for Scientific Research-Flanders (Research Grant No. 1510712N) and the University of Leuven (GOA/2011/03). B.S.B. acknowledges the Beckman Institute of the California Institute of Technology for support. We thank Stijn Van Cleuvenbergen for help with the spectral HRS measurement setup and Dr. Claire Lydon for assistance with the luminescence studies.
Funders:
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/J018635/1
Engineering and Physical Sciences Research Council (EPSRC)EP/K039547/1
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)1510712N
University of LeuvenGOA/2011/03
Caltech Beckman InstituteUNSPECIFIED
Hercules FoundationUNSPECIFIED
Issue or Number:9
Record Number:CaltechAUTHORS:20150615-115928582
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150615-115928582
Official Citation:Nonlinear Optical Chromophores with Two Ferrocenyl, Octamethylferrocenyl, or 4-(Diphenylamino)phenyl Groups Attached to Rhenium(I) or Zinc(II) Centers Benjamin J. Coe, Simon P. Foxon, Rachel A. Pilkington, Sergio Sánchez, Daniel Whittaker, Koen Clays, Griet Depotter, and Bruce S. Brunschwig Organometallics 2015 34 (9), 1701-1715 DOI: 10.1021/acs.organomet.5b00193
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58247
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:15 Jun 2015 21:30
Last Modified:03 Oct 2019 08:33

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