Nonlinear optical properties tuning in meso-tetraphenylporphyrin derivatives substituted with donor/acceptor groups in picosecond and nanosecond regimes.

Guanghong Ao,Xueru Zhang,Yuxiao Wang,Zhongguo Li,Yinglin Song,Zhengguo Xiao,Xuemin Qian

doi:10.3390/molecules20045554

Guanghong Ao, Xueru Zhang + Show 5 more

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https://doi.org/10.3390/molecules20045554

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Journal: Molecules (Basel, Switzerland)	Publication Date: Mar 27, 2015
Citations: 23	License type: CC BY 4.0

Affiliation: Harbin Institute of Technology

Abstract

meso-Tetraphenylporphyrin (TPP) and its two substituted derivatives (meso-tetrakis(4-cyanophenyl)porphyrin [TPP(CN)4] and meso-tetrakis(4-methoxyphenyl)porphyrin [TPP(OMe)4]) were synthesized. Their nonlinear absorption and refraction properties were studied using the Z-scan technique in the picosecond (ps) and nanosecond (ns) regimes. The open aperture Z-scan results reveal that TPP and TPP(CN)4 display an identical reverse saturable absorption (RSA) character in the ps and ns regimes. While TPP(OMe)4 exhibits a transition from saturable absorption (SA) to RSA in the ps regime and a typical RSA character in the ns regime. The closed aperture Z-scan results show that TPP(CN)4 and TPP(OMe)4 have regular enhancement of the magnitude of nonlinear refraction as compared to their parent TPP in both the ps and ns regimes. In addition, the second-order molecular hyperpolarizabilities (γ) of these three porphyrins are calculated, and the γ values of TPP(CN)4 and TPP(OMe)4 are remarkable larger than that of TPP. The introduction of the electron-withdrawing group CN and the electron-donating group OMe into TPP has enhanced its nonlinear refraction and γ value, and tuned its nonlinear absorption (TPP(OMe)4), which could be useful for porphyrin-related applications based on the desired NLO properties.

Highlights

Organic materials such as polymethine dyes [1], chromophores [2], phthalocyanines [3], porphyrins [4], and their related compounds [5] are target materials to study nonlinear optical (NLO) properties
To check the effect of CH2Cl2 solvent on the nonlinear absorption and refraction of the entire porphyrin/CH2Cl2 solution, the Z-scan measurements are first performed on CH2Cl2, as shown in
TPP and TPP(CN)4 both exhibit a notable valley at the focus, indicating a reverse saturable absorption (RSA) character with a positive nonlinear absorption coefficient

Summary

Introduction

Organic materials such as polymethine dyes [1], chromophores [2], phthalocyanines [3], porphyrins [4], and their related compounds [5] are target materials to study nonlinear optical (NLO) properties. Porphyrins are one of the attractive organic compounds with large nonlinear optical (NLO). The electronic structure of porphyrins can flexibly be tailored by the variation of peripheral substituents or the ligands of central atoms for tuning their NLO properties [5,15]. We reported our recent finding on the nonlinear absorption and refraction properties of mesotetraphenylporphyrin (TPP) and its two substituted derivatives (meso-tetrakis(4-cyanophenyl)porphyrin [TPP(CN)4] and meso-tetrakis(4-methoxyphenyl)porphyrin [TPP(OMe)4]) using the Z-scan technique in the picosecond (ps) and nanosecond (ns) regimes.

Linear Absorption Characterization

Picosecond Z-Scan Measurements

Nanosecond Z-Scan Measurements

Second-Order Molecular Hyperpolarizabilities

Experimental Section

Conclusions