Ultralarge hyperpolarizability twisted π-electron system electro-optic chromophores: Synthesis, solid-state and solution-phase structural characteristics, electronic structures, linear and nonlinear optical properties, and computational studies

被引：0

作者：

Kang, Hu ^{[1
]}

Facchetti, Antonio ^{[1
]}

Jiang, Hua ^{[1
]}

Cariati, Elena ^{[3
]}

Righetto, Stefania ^{[3
]}

Ugo, Renato ^{[3
]}

Zuccaccia, Cristiano ^{[4
]}

Macchioni, Alceo ^{[4
]}

Stern, Charlotte L. ^{[1
]}

Liu, Zhifu ^{[2
]}

Ho, Seng-Tiong ^{[2
]}

Brown, Eric C. ^{[1
]}

Ratner, Mark A. ^{[1
]}

Marks, Tobin J. ^{[1
]}

机构：

[1] Department of Chemistry, Materials Research Center, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, United States

[2] Department of Electrical and Computer Engineering, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, United States

[3] Dipartimento di Chimica Inorganica Metallorganica e Analitica, Centro di Eccellenza CIMAINA, Università di Milano, Via Venezian 21, I-20133 Milano, Italy

[4] Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto 8, I-06123 Perugia, Italy

来源：

Journal of the American Chemical Society | 2007年 / 129卷 / 11期

关键词：

This contribution details the synthesis and chemical/physical characterization of a series of unconventional twisted π-electron system electro-optic (EO) chromophores. Crystallographic analysis of these chromophores reveals large ring-ring dihedral twist angles (80-89°) and a highly charge-separated zwitterionic structure dominating the ground state. NOE NMR measurements of the twist angle in solution confirm that the solid-state twisting persists essentially unchanged in solution. Optical; IR; and NMR spectroscopic studies in both the solution phase and solid state further substantiate that the solid-state structural characteristics persist in solution. The aggregation of these highly polar zwitterions is investigated using several experimental techniques; including concentration-dependent optical and fluorescence spectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopy in combination with solid-state data. These studies reveal clear evidence of the formation of centrosymmetric aggregates in concentrated solutions and in the solid state and provide quantitative information on the extent of aggregation. Solution-phase DC electric-field-induced second-harmonic generation (EFISH) measurements reveal unprecedented hyperpolarizabilities (nonresonant πβ as high as -488 000 × 10-48 esu at 1907 nm). Incorporation of these chromophores into guest-host poled polyvinylphenol films provides very large electro-optic coefficients (r33) of 330 pm/V at 1310 nm. The aggregation and structure-property effects on the observed linear/nonlinear optical properties are discussed. High-level computations based on state-averaged complete active space self-consistent field (SA-CASSCF) methods provide a new rationale for these exceptional hyperpolarizabilities and demonstrate significant solvation effects on hyperpolarizabilities; in good agreement with experiment. As such; this work suggests new paradigms for molecular hyperpolarizabilities and electro-optics. © 2007 American Chemical Society;

D O I：

暂无

中图分类号：

学科分类号：

摘要：

Journal article (JA)

引用

页码：3267 / 3286

共 3 条

[1] Ultralarge hyperpolarizability twisted π-electron system electro-optic chromophores:: Synthesis, solid-state and solution-phase structural characteristics, electronic structures, linear and nonlinear optical properties, and computational studies
Kang, Hu
Facchetti, Antonio
Jiang, Hua
Cariati, Elena
Righetto, Stefania
Ugo, Renato
Zuccaccia, Cristiano
Macchioni, Alceo
Stern, Charlotte L.
Liu, Zhifu
Ho, Seng-Tiong
Brown, Eric C.
Ratner, Mark A.
Marks, Tobin J.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (11) : 3267 - 3286
[2] Ultralarge Hyperpolarizability, Novel Ladder-Type Heteroarenes Electro-Optic Chromophores: Influence of Fused Heterocyclic π-System and Push-Pull Effect on Nonlinear Optical Properties
Sun, Hejing
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2024, 124 (23)
[3] Design, synthesis, solid-state and solution structures, non linear optical and computational studies of copper(II) complexes supported by variously substituted enantiomerically pure push-pull tetradentate Schiff base ligands
Celedon, Salvador
Kahlal, Samia
Oyarce, Jocelyn
Cador, Olivier
Artigas, Vania
Fuentealba, Mauricio
Ledoux-Rak, Isabelle
Carrillo, David
Saillard, Jean-Yves
Hamon, Jean-Rene
Manzur, Carolina
JOURNAL OF MOLECULAR STRUCTURE, 2023, 1293

← 1 →