Synthesis, structure, linear and third-order nonlinear optical behavior of N-(3-hydroxybenzalidene)4-bromoaniline

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Abstract

N-(3-Hydroxybenzalidene)4-bromoaniline has been synthesized. Its crystal structure has been determined by X-ray diffraction analysis. To investigate microscopic third-order nonlinear optical (NLO) behavior of the title compound, we have computed both dispersion-free (static) and also frequency-dependent (dynamic) linear polarizabilities (α) and second hyperpolarizabilities (γ) at λ = 825–1125 nm and 1050–1600 nm wavelength areas using time-dependent Hartree–Fock (TDHF) method. The one-photon absorption (OPA) characterization has been theoretically obtained by means of configuration interaction (CI) method. The maximum OPA wavelengths are estimated in the UV region to be shorter than 450 nm, showing good optical transparency to the visible light. According to ab-initio calculation results on (hyper)polarizabilities, the synthesized molecule exhibits second hyperpolarizabilities with non-zero values, and it might have microscopic third-order NLO behavior.

Introduction

Nonlinear optical (NLO) materials have been extensively studied for many years [1], [2], [3], [4], [5]. The search of new materials which have NLO properties is an important research field [6]. Significant interest still exists in the design and development of materials exhibiting large second-order NLO response because of the potential application in telecommunications, optical computing and optical signal processing [7], [8], [9], [10]. Actually, the third-order response governed by the second hyperpolarizability offers more varied and richer behavior than the second-order NLO process due to the higher dimensionality of the frequency space. In the light of wide applications of NLO effects, a large number of materials have been synthesized and their NLO properties have been explored using different techniques like degenerate four-wave mixing, Z-scan and third-harmonic generation (THG). THG measurements are particularly interesting since they are strongly related to electronic processes. For the free molecule, accurately determined experimental dipole and quadrupole moments and the (hyper)polarizabilities are known and could be reproduced by ab-initio calculations, if reasonably high correlation levels and large basis sets have been used [11], [12], [13]. However, experimental determination of the corresponding effective properties in condensed phases is much more difficult and rests on a number of assumptions and approximations whose limitations are difficult to assess.

Due to their centrosymmetric structures, non-substituted or symmetrically substituted organic compounds have been basically studied as third-order NLO materials. One could expect that the title Schiff base compound based on a centrosymmetric structure (Fig. 1) may show third-order NLO behavior. Theoretical calculations offer a quick and inexpensive way of predicting the NLO responses of the materials especially during the design of the new materials. Therefore, the present paper aims to give a contribution to the knowledge of the third-order optical nonlinearity of the synthesized and characterized (X-ray structure determination) title molecule by computing the maximum one-photon absorption (OPA) wavelengths and (hyper)polarizabilities with configuration interaction (CI) and ab-initio time-dependent Hartree–Fock (TDHF) methods.

Section snippets

Preparation of N-(3-hydroxybenzalidene)4-bromoaniline

The title compound was prepared by the addition of 0.01 mol of 4-bromo-aniline in 60 ml of hot ethanol to 0.01 mol of 3-hydroxy-benzaldehyde in 80 ml of boiling ethanol, followed by heating to reflux for 4 h. Yellow crystals, suitable for X-ray analysis, were formed during reflux; found: C, 56.40%; H, 3.33%; N, 4.94%. C13H10BrNO: C, 56.55%; H, 3.65%; N, 5.07%.

X-ray structure determination

A suitable sample of size, for the title compound, 0.06 × 0.16 × 0.44 mm was chosen for the crystallographic study and then carefully mounted on

Theoretical calculations

The theoretical computations involve the determination of dispersion-free and frequency-dependent linear polarizability and second hyperpolarizability tensor components of the title compound using the following methods.

As the first step of static and dynamic (hyper)polarizability calculations, the geometries taken from the starting structures in Table 2 have been optimized in the ab-initio restricted Hartree–Fock level. The optimized structures have been used to compute the linear

Description of the crystal structure

Conjugated organic molecules containing both donor and acceptor groups are of great interest for molecular electronic devices. Second-order NLO organic materials, which contain stable molecules with large molecular hyperpolarizabilities in non-centrosymmetric packing, are of great interest for device applications [26], but according to a statistical study, an overwhelming majority of achiral molecules crystallize centrosymmetrically [27].

The title molecule is not planar. Schiff base moieties A

Conclusions

The title compound has been synthesized for the study of its third-order optical nonlinearity. The structural characterization has been investigated by X-ray diffraction measurements. To understand the relationship between structure–property and NLO, we have extended our study to compute the OPA wavelengths, linear and second (hyper)polarizabilities using CI and TDHF methods. According to the calculation results on the linear optical behavior, the synthesized molecule is almost transparent in

Acknowledgement

This work was supported by Turkish State of Planning Organization (DPT), TUBİTAK and Selçuk University under Grant Nos. 2003-K-12019010-7, 105T132, and 2003/030, respectively.

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