TY - JOUR
T1 - Facile structure and property tuning through alteration of ring structures in conformationally locked phenyltetraene nonlinear optical chromophores
AU - Zhou, Xing Hua
AU - Davies, Joshua
AU - Huang, Su
AU - Luo, Jingdong
AU - Shi, Zhengwei
AU - Polishak, Brent
AU - Cheng, Yen-Ju
AU - Kim, Tae Dong
AU - Johnson, Lewis
AU - Jen, Alex
PY - 2011/3/28
Y1 - 2011/3/28
N2 -
A series of phenyltetraene-based nonlinear optical (NLO) chromophores 1a-c with the same donor and acceptor groups, but different tetraene bridges that are partly connected by various sizes of aliphatic rings, have been synthesized and systematically investigated. The interposed conjugated tetraene segments in three chromophores studied are based on isophorone, (1S)-(-)-verbenone, and 3,4,4-trimethyl-2-cyclopentenone, respectively. This kind of structural alteration has significant effect on the intrinsic electronic structures and physical properties of these highly polarizable chromophores as revealed by a variety of characterization techniques. The introduction of the verbenone- and trimethylcyclopentenone-based tetraene bridges could significantly improve the glass-forming ability of chromophores 1b and 1c in comparison with the highly crystalline characteristics of isophorone-based chromophores 1a. More importantly, chromophores 1a-c exhibited distinct optical features in absorption band shape, solvatochromic behavior, as well as energy band gap from the UV-vis-NIR absorption measurements. Quantum mechanical calculations using density functional theory (DFT) were also used to evaluate second-order NLO properties of these chromophores. The electro-optic (EO) coefficients of 1a-c in poled polymers with the 10 wt% chromophore content showed an apparent decrease from 78 pm V
-1
for 1a to 42 pm V
-1
for 1c. This decrease is attributed to the gradual decrease of the molecular hyperpolarizability (β) of the chromophores which is associated with the progressive cyanine-like electronic structure from the isophorone-based 1a to the cyclopentenone-based 1c chromophore.
AB -
A series of phenyltetraene-based nonlinear optical (NLO) chromophores 1a-c with the same donor and acceptor groups, but different tetraene bridges that are partly connected by various sizes of aliphatic rings, have been synthesized and systematically investigated. The interposed conjugated tetraene segments in three chromophores studied are based on isophorone, (1S)-(-)-verbenone, and 3,4,4-trimethyl-2-cyclopentenone, respectively. This kind of structural alteration has significant effect on the intrinsic electronic structures and physical properties of these highly polarizable chromophores as revealed by a variety of characterization techniques. The introduction of the verbenone- and trimethylcyclopentenone-based tetraene bridges could significantly improve the glass-forming ability of chromophores 1b and 1c in comparison with the highly crystalline characteristics of isophorone-based chromophores 1a. More importantly, chromophores 1a-c exhibited distinct optical features in absorption band shape, solvatochromic behavior, as well as energy band gap from the UV-vis-NIR absorption measurements. Quantum mechanical calculations using density functional theory (DFT) were also used to evaluate second-order NLO properties of these chromophores. The electro-optic (EO) coefficients of 1a-c in poled polymers with the 10 wt% chromophore content showed an apparent decrease from 78 pm V
-1
for 1a to 42 pm V
-1
for 1c. This decrease is attributed to the gradual decrease of the molecular hyperpolarizability (β) of the chromophores which is associated with the progressive cyanine-like electronic structure from the isophorone-based 1a to the cyclopentenone-based 1c chromophore.
UR - http://www.scopus.com/inward/record.url?scp=79952584197&partnerID=8YFLogxK
U2 - 10.1039/c0jm02855j
DO - 10.1039/c0jm02855j
M3 - Article
AN - SCOPUS:79952584197
VL - 21
SP - 4437
EP - 4444
JO - Journal of Materials Chemistry
JF - Journal of Materials Chemistry
SN - 0959-9428
IS - 12
ER -