Organic Salts Suppress Aggregation and Enhance the Hyperpolarizability of a π‐Twisted Chromophore

Abstract

Twisted intramolecular charge‐transfer (TICT) chromophores exhibit extraordinary hyperpolarizabilities, β, and are therefore promising for electro‐optic technologies. Nevertheless, centrosymmetric aggregate formation severely diminishes β in concentrated solutions or in polymer matrices. Herein, the remarkable effects of organic salts on the linear and nonlinear optical response of a high β benzimidazolium‐based TICT chromophore, B2TMC‐2, are reported. Addition of Bu4P+Br− to B2TMC‐2 solution in CHCl3 induces a halochromic blueshift, primarily reflecting interactions between Bu4P+Br− and the B2TMC‐2 cationic portion. DC electric‐field induced second‐harmonic generation (EFISH) measurements on B2TMC‐2+Bu4P+Br− solution reveal a large μβ=−22,160×10−48 esu, unprecedented for any chromophore with such a broad optical transparency window. Moreover, Bu4P+Br− is shown to suppress B2TMC‐2 aggregation, thereby preserving high μβ in concentrated solutions. This phenomenon should be applicable to many other NLO chromophores.

Document Details

Document Type
Pub Defense Publication
Publication Date
Oct 01, 2018
Source ID
10.1002/chem.201804365

Entities

People

  • Alexander J.‐t. Lou
  • Elena Cariati
  • Stefania Righetto
  • Tobin J. Marks

Organizations

  • Air Force Office of Scientific Research
  • Northwestern University
  • University of Milan

Tags

Fields of Study

  • Chemistry

Readers

  • Chemistry (specifically Chemical Fluorescence)
  • Electrochemical Engineering/ Fuel Cell Technologies
  • Optical Physics and Photonics.