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Rhenium(I) Tricarbonyl Complexes with Peripheral N-Coordination Sites: A Foundation for Heterotrimetallic Nonlinear Optical Chromophores

Coe, Benjamin J. and Foxon, Simon P. and Pilkington, Rachel A. and Sánchez, Sergio and Whittaker, Daniel and Clays, Koen and Van Steerteghem, Nick and Brunschwig, Bruce S. (2016) Rhenium(I) Tricarbonyl Complexes with Peripheral N-Coordination Sites: A Foundation for Heterotrimetallic Nonlinear Optical Chromophores. Organometallics, 35 (17). pp. 3014-3024. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20161007-114720215

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Abstract

The compounds 4,4′-dicyano-2,2′-bipyridyl (dcbpy), 4,4′-bis(4-cyanophenyl)-2,2′-bipyridyl (bcpbpy), 4,4′-bis[(E)-2-(4-cyanophenyl)vinyl]-2,2′-bipyridyl (bcpvbpy), and 4,4′-bis[(E)-2-(4-pyridyl)vinyl]-2,2′-bipyridyl (bpvbpy) are used to prepare nine new complexes with fac-{Re^I(CO)_3(L)}^(n+) (L = Cl^–, MeCN, pyridine (py), or 4-cyanopyridine (cpy)) centers. The cationic complexes are isolated as their OTf^– salts. These new monometallic species are studied together with the known fac-Re^ICl(CO)_3(qpy) (qpy = 4,4′:2′,2″:4″,4‴-quaterpyridyl) (de Wolf, P.; et al. Inorg. Chim. Acta 2003, 355, 280–285). Coordination of {Ru^(II)(NH_3)_5}^(2+) centers to the peripheral N atoms of fac-Re^ICl(CO)_3(qpy) and fac-[Re^I(CO)_3(bcpbpy)(py)]^+ affords heterotrimetallic complexes that are isolated as their PF_6^– salts. Single-crystal X-ray structures are reported for the solvates fac-Re^ICl(CO)_3(dcbpy)·Me_2CO, fac-[Re^I(CO)_3(dcbpy)(MeCN)]OTf·PhMe, fac-[Re^I(CO)_3(dcbpy)(py)]OTf·0.5PhMe, fac-[ReI(CO)3(dcbpy)(cpy)]OTf·0.5Me2CO, fac-Re^ICl(CO)_3(bcpbpy)·0.5PhMe, and fac-[Re^I(CO)_3(bcpbpy)(MeCN)]OTf·MeCN. Cyclic voltammetry reveals irreversible ReII/I processes in all cases, while the trimetallic compounds show a reversible two-electron RuIII/II oxidation wave. Ligand-based reductions are generally irreversible, but reversible waves are observed for the dcbpy complexes. Electronic absorption spectra show strong d → π^* metal-to-ligand charge-transfer (MLCT) and intraligand π → π^* absorptions. The Ru^(II)-based MLCT bands have lower energies and higher intensities than the ReI-based ones. The monometallic species emit weakly in the red/NIR region (λ_(em) = 594–732 nm; ϕ = 0.6–8.1%) when excited at 350–520 nm. Molecular first hyperpolarizabilities β for the trimetallic complex salts are measured in MeCN solutions via the hyper-Rayleigh scattering technique at 1064 nm. Stark (electroabsorption) spectroscopic studies on the low-energy MLCT bands in frozen PrCN allow the indirect estimation of static first hyperpolarizabilities β_0. The trimetallic complexes have relatively large β_0 values, ca. 500 × 10^(–30) esu or more, which are substantially greater than those of the monometallic species.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.organomet.6b00536DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.6b00536PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.organomet.6b00536PublisherSupporting Information
ORCID:
AuthorORCID
Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2016 American Chemical Society. Received: July 1, 2016. Published: August 23, 2016. We thank the EPSRC (a Ph.D. studentship for R.A.P. and grants EP/D070732/1, EP/J018635/1, and EP/K039547/1), the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), and the University of Leuven (GOA/2011/03) for support. B.S.B. acknowledges the Beckman Institute of the California Institute of Technology for support. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/D070732/1
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)FWO-V, G.0312.08
University of LeuvenGOA/2011/03
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:17
Record Number:CaltechAUTHORS:20161007-114720215
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20161007-114720215
Official Citation:Rhenium(I) Tricarbonyl Complexes with Peripheral N-Coordination Sites: A Foundation for Heterotrimetallic Nonlinear Optical Chromophores Benjamin J. Coe, Simon P. Foxon, Rachel A. Pilkington, Sergio Sánchez, Daniel Whittaker, Koen Clays, Nick Van Steerteghem, and Bruce S. Brunschwig Organometallics 2016 35 (17), 3014-3024 DOI: 10.1021/acs.organomet.6b00536
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70954
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:12 Oct 2016 22:12
Last Modified:03 Oct 2019 16:02

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