Nonlinear Optical and Related Properties of Iron(II) Pentacyanide Complexes with Quaternary Nitrogen Electron Acceptor Units
Abstract
Three new complex salts Na_2[Fe^(II)(CN)_5(L)] [L ) N-methyl-4-{E,E-4-(4-pyridyl)buta-1,3-dienyl}pyridinium, N-methyl- 4-{E,E,E-6-(4-pyridyl)hexa-1,3,5-trienyl}pyridinium, or N-methyl-1,4-bis-{E-2-(4-pyridyl)ethenyl}] benzene have been prepared. These compounds have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry, allowing their properties to be compared with those of the known complexes where L = N-methylpyrazinium (Mepyz^+), N-methyl-4,4^′-bipyridinium, or N-methyl-4-[E-2-(4-pyridyl)ethenyl]pyridinium. Molecular quadratic nonlinear optical (NLO) responses have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d f π^* metal-to-ligand charge-transfer (MLCT) bands. The MLCT transitions show large red-shifts on moving from aqueous to methanol solutions, and these excitations are associated with relatively large static first hyperpolarizabilities β_0. Single crystal X-ray structures of two hydrated materials containing the complex anion [Fe^(II)(CN)_5(Mepyz^+)]^(2-) have been determined, and both of these show some degree of alignment of the constituent complex dipoles.
Additional Information
© 2009 American Chemical Society. Published on Web 01/12/2009. Note Added after ASAP Publication. There was an error in a formula within the Crystallographic Studies section in the version that published on January 12, 2009. The corrected version was published ASAP on January 21, 2009. We thank the EPSRC for support in the form of PhD studentships (E.C.H. and C.A.S.) and a postdoctoral grant (SPF, EP/D070732), and also the Fund for Scientific Research-Flanders (FWO-V, G.0297.04), the University of Leuven (GOA/2006/3), and the Belgian Government (IUAP P5/3). Supporting Information Available: X-ray crystallographic data in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.Attached Files
Supplemental Material - ic801224u_si_001.cif
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Additional details
- Eprint ID
- 15165
- Resolver ID
- CaltechAUTHORS:20090819-092202120
- EP/D070732
- Engineering and Physical Sciences Research Council (EPSRC)
- G.0297.04
- Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)
- GOA/2006/3
- University of Leuven
- IUAP P5/3
- Belgian Government
- Created
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2009-08-19Created from EPrint's datestamp field
- Updated
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2021-11-08Created from EPrint's last_modified field