Photoisomerization-switchable second-order nonlinear optical responses of dithienylethene-containing boron derivatives: a theoretical study

2015 ◽  
Vol 93 (3) ◽  
pp. 297-302 ◽  
Author(s):  
Hailing Yu ◽  
Bo Hong ◽  
Yunqing Luo ◽  
Hongyan Zhao
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Second Order ◽  
Boron Compounds ◽  
Functional Theory ◽  
Optical Responses ◽  
Closed Ring ◽  
Open Ring ◽  
Optical Behavior ◽  
Degree Of Charge Transfer

The switchable second-order nonlinear optical properties of a series of dithienylethene-containing boron compounds possessing reversible photochromic behavior have been systemically investigated based on density functional theory. The significant differences on the static first hyperpolarizabilities caused by the photoisomerization reaction confirm the switchable nonlinear optical behavior. Results show that the closed-ring 1c–4c possess large static first hyperpolarizabilitieswith respect to their corresponding open-ring 1o–4o, which is due to the better π-conjugation and a more obvious degree of charge transfer. Specifically, the static first hyperpolarizability values increase in the range of 2.4–5.2 times with the strengthening electron-withdrawing ability of the substituent R (R = H, CF3, NO2) on the pyridine and elongating the conjugated chains. It indicates that introducing boron-based functional groups to the dithienylethene monomer and modifying the pyridine ring can effectively improve the switching nonlinear optical responses.

THEORETICAL INVESTIGATION ON PHOTOISOMERIZATION SWITCHABLE SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF Λ-SHAPED DIARYLETHENE DERIVATIVES

2013 ◽  
Vol 12 (04) ◽  
pp. 1350029 ◽  
Author(s):  
XIAOFENG DU ◽  
NANA MA ◽  
SHILING SUN ◽  
HAIMING XIE ◽  
YONGQING QIU
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Nonlinear Optical ◽  
Frontier Molecular Orbital ◽  
Dft Methods ◽  
Functional Theory ◽  
Ring Molecules ◽  
Closed Ring ◽  
Open Ring ◽  
Nlo Switching

The nonlinear optical (NLO) properties of Λ-shaped diarylethene (DAE) derivatives 1a(b)–4a(b) and their NLO switching effects were studied by using the density functional theory (DFT) methods. The results demonstrate that all of the open-ring molecules and their own closed-ring forms meet the model of NLO switching tuned by photoisomerization. The βtot values of 1b–3b are 16 times as small as that of their open-ring forms, and βtot value of 4b is 4 times as large as that of 4a. The spin interactions of open-shell closed-ring molecules are larger than that of their open-ring forms, and it could increase the NLO responses to some degree. Nature bond orbital (NBO) calculations indicate that large charge differences between electron-deficient and electron-rich centers are beneficial to charge transfer (CT), and the overlap between frontier molecular orbital (FMO) is also advantageous to the CT and NLO responses. Time-dependent density functional theory (TD-DFT) calculations show βtot values of all molecules meet the two-level model very well, and the smaller the ΔE ge , the larger the βtot value.

Switchable second-order nonlinear optical response of platinum-sensitized dithienylethenes

2019 ◽  
Vol 18 (04) ◽  
pp. 1950022
Author(s):  
Xiao-Yun Liu ◽  
Zhi-Yuan Shi ◽  
Jin-Ting Ye ◽  
Hui-Ying Wang ◽  
Hong-Qiang Wang ◽  
...  
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Dft Method ◽  
Second Order ◽  
Computational Formula ◽  
Functional Theory ◽  
Nlo Properties ◽  
Closed Ring ◽  
The Density Functional Theory ◽  
Ring Complexes

The electronic structure and the nonlinear optical (NLO) properties of a series of platinum-sensitized dithienylethenes (DTEs) were investigated by using the density functional theory (DFT) method. DFT calculations reveal that the second-order NLO properties of complexes significantly increase with the DTE ligand being directly linked with terpyridine–Pt(II) complexes. Due to the good [Formula: see text]-conjugated characteristics, closed-ring complexes possess much larger second-order NLO properties than the corresponding open-ring complexes. The computational [Formula: see text] values are in the order of 3c ([Formula: see text] esu) [Formula: see text] 3o ([Formula: see text] esu) [Formula: see text] 4c ([Formula: see text] esu) [Formula: see text] 4o ([Formula: see text] esu) [Formula: see text] 1 ([Formula: see text] esu) [Formula: see text] 2c ([Formula: see text] esu) [Formula: see text] 2o ([Formula: see text] esu). Among all calculated platinum-sensitized dithienylethenes, 3c has the largest second-order NLO properties. The 4c and 4o have almost the same [Formula: see text] values and the [Formula: see text] value of 4o is slightly larger than that of 2o because the ether bonds can significantly prevent charge transfer within the complexes.

Computational study on redox-switchable second-order nonlinear optical properties of ferrocene-tetrathiafulvalene hybrid

RSC Advances ◽  
2014 ◽  
Vol 4 (72) ◽  
pp. 38300-38309 ◽  
Author(s):  
Chun-Guang Liu ◽  
Ming-Li Gao ◽  
Zhi-Jian Wu
Keyword(s):  
Density Functional Theory ◽  
Optical Properties ◽  
Density Functional ◽  
Nonlinear Optical ◽  
Computational Study ◽  
Density Functional Theory Calculations ◽  
Second Order ◽  
Nonlinear Optical Properties ◽  
Functional Theory

Redox-switchable second-order nonlinear optical (NLO) responses of a series of ferrocene-tetrathiafulvalene (Fc–TTF) hybrids have been studied based on density functional theory calculations.

THEORETICAL STUDY ON THE SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF C,B-SUBSTITUTED CARBORANE CONJUGATED DERIVATIVES

2012 ◽  
Vol 11 (05) ◽  
pp. 1121-1133 ◽  
Author(s):  
YAN LIU ◽  
GUOCHUN YANG ◽  
SHILING SUN ◽  
FEI YU ◽  
ZHONGMIN SU ◽  
...  
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Transition Energy ◽  
Energy Transition ◽  
Second Order ◽  
Orbital Energy ◽  
First Hyperpolarizability ◽  
Structure Property ◽  
Functional Theory ◽  
Nlo Materials

To systemically investigate structure–property relationship and design excellent nonlinear optical (NLO) material, the second-order NLO properties of a series of C,B -substituted carborane conjugated derivatives have been studied by density functional theory (DFT). The static first hyperpolarizabilities (βtot) were calculated at the M05-2X/6-31+G* level of theory. The results show that the βtot values gradually increase with the increasing of the conjugation length, especially the introduction of ferrocene. It is found that 1,3-benzo-o-carborane-ferrocene (2h) has the largest first hyperpolarizability (55.968 × 10-30 esu), which is 150 times larger than that of benzocarborane (1a). This means that the static first hyperpolarizabilities of the studied compounds can be substantially increased by structural modification. A basis for understanding the origin of these large NLO responses is proposed based on consideration of the frontier molecular orbitals (FMOs), orbital energy, transition energy of the studied compounds, and the two-state mode. The lower transition energy and larger oscillator strength play an important role in increasing the first hyperpolarizability value. This study may evoke possible ways to design preferable NLO materials.

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