CaltechAUTHORS
Published March 4, 2016 | Version Published + Supplemental Material
Journal Article Open

Helquat Dyes: Helicene-like Push–Pull Systems with Large Second-Order Nonlinear Optical Responses

Creators

  • 1. ROR icon University of Manchester
  • 2. ROR icon Institute of Organic Chemistry and Biochemistry
  • 3. ROR icon Charles University
  • 4. ROR icon KU Leuven
  • 5. ROR icon California Institute of Technology

Abstract

Helquat dyes combine a cationic hemicyanine with a helicene-like motif to form a new blueprint for chiral systems with large and tunable nonlinear optical (NLO) properties. We report a series of such species with characterization, including determination of static first hyperpolarizabilities β_0 via hyper-Rayleigh scattering and Stark spectroscopy. The measured β_0 values are similar to or substantially larger than that of the commercial chromophore E-4′-(dimethylamino)-N-methyl-4-stilbazolium. Density functional theory (DFT) and time-dependent DFT calculations on two of the new cations are used to probe their molecular electronic structures and optical properties. Related molecules are expected to show bulk second-order NLO effects in even nonpolar media, overcoming a key challenge in developing useful materials.

Additional Information

© 2016 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: December 2, 2015; Published: February 4, 2016. This work was supported by ASCR (RVO: 61388963, M200551208 to F.T.), the Czech Science Foundation (13-19213S to F.T.), the Fund for Scientific Research-Flanders (Research Grant 1510712N), the University of Leuven (GOA/2011/03), and the EPSRC (grants EP/G020299/1 and EP/J018635/1 to B.J.C.). B.S.B. acknowledges the Beckman Institute of the California Institute of Technology for support. We thank Mrs. J. Bařinková for her skillful experimental help. The authors declare no competing financial interest.

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Published - acs_2Ejoc_2E5b02692.pdf

Supplemental Material - jo5b02692_si_001.pdf

Supplemental Material - jo5b02692_si_002.cif

Supplemental Material - jo5b02692_si_003.cif

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Additional details

Identifiers

Eprint ID
65386
Resolver ID
CaltechAUTHORS:20160316-082203585

Funding

Academy of Sciences of the Czech Republic
61388963
Academy of Sciences of the Czech Republic
M200551208
Czech Science Foundation
13-19213S
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)
1510712N
University of Leuven
GOA/2011/03
Engineering and Physical Sciences Research Council (EPSRC)
EP/G020299/1
Engineering and Physical Sciences Research Council (EPSRC)
EP/J018635/1
Caltech Beckman Institute

Dates

Created
2016-03-16
Created from EPrint's datestamp field
Updated
2021-11-10
Created from EPrint's last_modified field