Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 75, Issue 24, Pages 8550-8563Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo101966r
Keywords
-
Categories
Funding
- EPSRC [EP/E000738, EP/D070732]
- Fund for Scientific Research-Flanders [FWO-V, G.0312.08]
- University of Leuven [GOA/2006/3]
- NSF [CHE-0802907]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0802907] Funding Source: National Science Foundation
- EPSRC [EP/E000738/1, EP/D070732/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/E000738/1, EP/D070732/1] Funding Source: researchfish
Ask authors/readers for more resources
Six new dicationic 2D nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by nucleophilic substitutions of 2,6-dichloropyrazine with pyridyl derivatives. These compounds have been characterized as their PF6- salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Large red shifts in the intense, pi -> pi* intramolecular charge-transfer (ICT) transitions on replacing -oMe with -NMe2 substituents arise from the stronger pi-electron donor ability of the latter. Each compound shows a number of redox processes which are largely irreversible. Single crystal X-ray structures have been determined for five salts, including two nitrates, all of which adopt centrosymmetric packing arrangements. Molecular first hyperpolarizabilities beta have been determined by using femtosecond hyper-Rayleigh scattering at 880 and 800 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly 2D, with dominant off-diagonal beta(zyy) components. Stark (electroabsorption) spectroscopic measurements on the ICT bands afford estimated static first hyperpolarizabilities beta(0). The directly and indirectly derived beta values are large, and the Stark-derived beta(0) response for one of the new salts is several times greater than that determined for (E)4'-(dimethylamino)-N-methyl-4-stilbazolium hexafluorophosphate. These Stark spectroscopic studies also permit quantitative comparisons with related 2D, binuclear Ru-II ammine complex salts.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available