TY - JOUR
T1 - Nonlinear optical and related properties of iron(II) pentacyanide complexes with quaternary nitrogen electron acceptor units
AU - Coe, Benjamin J.
AU - Foxon, Simon P.
AU - Harper, Elizabeth C.
AU - Raftery, James
AU - Shaw, Rachel
AU - Swanson, Catherine A.
AU - Asselberghs, Inge
AU - Clays, Koen
AU - Brunschwig, Bruce S.
AU - Fitch, Anthony G.
PY - 2009/2/16
Y1 - 2009/2/16
N2 - 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 → 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. © 2009 American Chemical Society.
AB - 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 → 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. © 2009 American Chemical Society.
UR - https://www.scopus.com/pages/publications/64349100442
U2 - 10.1021/ic801224u
DO - 10.1021/ic801224u
M3 - Article
SN - 0020-1669
VL - 48
SP - 1370
EP - 1379
JO - Inorganic Chemistry: including bioinorganic chemistry
JF - Inorganic Chemistry: including bioinorganic chemistry
IS - 4
ER -