Theoretical study of nonlinear optical properties of oxocarbon derivatives

Junqueira, Geórgia M. A.; Faria, M. S.; Silva, A. M. Da; Santos, Hélio F. Dos

doi:10.1002/qua.22088

Cited by 7 publications

(4 citation statements)

References 58 publications

(98 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The Hammett sigma constant is an empirical parameter for understanding the structure–property relationship among a series of derivatives with various substituents. Some linear or nonlinear correlations between the second‐order polarizabilities and σ values have been demonstrated by phthalocyanines,39 triazine derivatives,40, 41 metallabenzene‐based chromophores,42 azo dyes,43 and oxocarbon derivatives44. In Fig.…”

Section: Resultsmentioning

confidence: 89%

Tuning the absorption spectra and nonlinear optical properties of D‐π‐A azobenzene derivatives by changing the dipole moment and conjugation length: a theoretical study

Liu¹,

Lu²,

Ma³

2010

J of Physical Organic Chem

View full text Add to dashboard Cite

The optical properties of several azobenzene derivatives were modulated by varying the dipole moments and conjugation lengths of the D‐π‐A systems. The relationship between the structure and absorption spectrum and polarizability was studied in the gas phase, THF and MeOH solutions, respectively, by using the density functional theory. The calculated absorption spectra and second‐order polarizabilities are in good agreement with the available experimental observations. In comparison with the D‐π‐A monomer, the H‐shaped D‐π‐A dimer almost doubles the dipole moments and hence increases the second‐order polarizabilities, without a significant shift in the maximum absorption bands. The addition of another azobenzol group between electron‐donating and ‐accepting groups increases the second‐order polarizabilities by 4–6 times, but leads to an evident red‐shift of about 65–80 nm in spectra. The relative second‐order polarizability of the halogen‐substituted derivatives is in the sequence of CF3 > F > Cl > Br, without obvious substituent effects on the optical transparency. The D‐π‐A chromophores with the strong electron‐donating (amino) and ‐accepting (acetyl) substituent present the larger second‐order polarizabilities, at the cost of about 20 nm red‐shift of the maximum absorption lengths relative to the halogen‐substituted species. It is also demonstrated that both the linear and nonlinear optical properties augment with the increase in solvent polarity, accompanied by a red‐shift in the wavelengths of maximum absorption by about 18 and 23 nm, respectively, in THF and MeOH solutions. The changes in optical properties upon the structural modifications are further rationalized by the electronic structures of various H‐shaped dimers. Copyright © 2010 John Wiley & Sons, Ltd.

show abstract

Section: Resultsmentioning

confidence: 89%

Tuning the absorption spectra and nonlinear optical properties of D‐π‐A azobenzene derivatives by changing the dipole moment and conjugation length: a theoretical study

Liu¹,

Lu²,

Ma³

2010

J of Physical Organic Chem

View full text Add to dashboard Cite

show abstract

“…Here this global parameter covers a (2) [8,[42][43][44][45][46] have reported relationships among NLO quantities and some Hammett electronic parameters [32]. In a previous study [8], we found that β tot values of the 1,12-(para-) dicarba-closo-dodecarboranes push-pull compounds were enhanced by two orders of magnitude when compared to unsubstituted dodecarboranes.…”

Section: Resultsmentioning

confidence: 92%

Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents

Junqueira

Sato

2015

Theor Chem Acc

View full text Add to dashboard Cite

interesting feature of the boron-based cages, due to high electronic and thermal stability, delocalized structures and easy functionalization, is the potential application in nonlinear optics (NLO) [3,5,21]. Generally, molecules with NLO applications are systems with acceptor and donor electron groups in its extremities (push-pull type), high values of first-order hyperpolarizability (β) and permanent dipole moment (d). The second-order responses can be enhanced by increasing the electronic asymmetry or the conjugation length between the extremity groups [22,23]. Besides, the structure must be non-centrosymmetric, and the molecules must present absorption at wavelength greater than 400 nm for second harmonic generation (SHG), to avoid re-absorption of the converted light [24]. The energy (E) of a molecular system under an external electric field F can be written as Eq. (1), where E(0) is the energy of the system in the absence of an external field, and F i are the components of the applied field [25]:The dipole moment (d), the linear polarizability (α), and the first-and second-order hyperpolarizabilities (β and γ) play a significant role mainly in the study of NLO properties [24,26,27].The NLO behavior of icosahedral carboranes has been investigated for more than 20 years [14]. Studies in this area involving carboranes include synthesis of novel compounds [14,18] and NLO properties' calculations [5,8,[15][16][17]21,28]. For example, a new class of dodecarboranes ([B 12 H 11 -C 2 B 10 H 11 ] 2− ) with potential application as NLO materials was proposed through ab initio calculations (1)In the present work, molecular first-order hyperpolarizability (β tot ) and dipole moment (d) are obtained at B3LYP/6-31G(d,p) level of theory by coupled perturbed Hartree-Fock method within the static approach. The investigated molecules are a series of substituted cobalt bis (dicarbollide) derivatives: Hydrogens bonded to the two carbon atoms are replaced by acceptor and donor electron substituents. Correlations between the Hammett electronic parameters of the substituents and the molecular properties are tested. Among them, the named push-pull compounds produced the largest calculated values of β tot and d. The UV-Vis spectra are reported for all studied compounds.

show abstract

“…It has also been shown that the nonlinear properties can be estimated with increased accuracy through the use of post‐Hatree–Fock (post‐HF) methods. However, semiempirical (Parametric Method 3 (PM3) and AM1), HF, and density functional theory (DFT) approaches have also been satisfactorily applied to relatively large molecules, for which more rigorous methods such as n th‐order Møller–Plesset perturbation theory (MPn) and coupled cluster (CC) are prohibitive 2, 21, 44, 45. The choice of the basis set also plays a role in the quality of the results.…”

Section: Introductionmentioning

confidence: 99%

“…According to the literature, calculations using a large basis set with polarization and diffuse functions are required to reproduce the experimental magnitude of β 2, 44, 46. Nonetheless, several systematic theoretical studies indicate that the inclusion of an augmented set does not promote large differences in the β values for extended systems, with calculated values being in accordance with the experimental data even when medium‐size basis sets are used 2, 44–48. Furthermore, for very large molecules, such as those studied in this work, the small 6‐31G(d) basis set seems to be appropriate for structural determination as well as for calculation of the hyperpolarizability, because our main goal is to screen molecules with enhanced nonlinear responses within a specific class of compounds.…”

Section: Introductionmentioning

confidence: 99%

Donor–acceptor diethynylsilane oligomers: A second‐order nonlinear optical material

Machado

Souza

Santos

et al. 2011

J Polym Sci B Polym Phys

View full text Add to dashboard Cite

The interest in the study of oligomers has been motivated mainly because of their solubility in common solvents and also their capacity to be crystallized, which allowed for chemical processing leading to important applications in the area of material sciences. In this work, we carried out an investigation of polydiethynylsilane (PDES) decamers substituted with electron donor (D) and acceptor (A) groups, which is certainly of relevance, once PDES itself is known to display large third‐order optical susceptibility. Therefore, density functional theory calculations of static first hyperpolarizability (β) were performed using various functionals with the 6‐31G(d) basis set along with correlated MP2 calculation used as reference for comparison. The influence of A and D substituents on the magnitude of β was investigated by matching the acceptor (dicyanovinyl, nitrobenzene) and donor (propyl, propoxy, and phenylamine) groups attached at both ends of the oligomer. The largest β value was predicted for the derivative having the phenylamine and dicyanovinyl groups, which is around 30 times the relative value for the nonsubstituted decamer, what is a very impressive enhancement reported for the first time in the literature, strongly suggesting that disubstituted diethynylsilane decamers are potential building blocks for molecular‐based materials with second‐order nonlinear responses. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1410–1419, 2011

show abstract

Theoretical study of nonlinear optical properties of oxocarbon derivatives

Cited by 7 publications

References 58 publications

Tuning the absorption spectra and nonlinear optical properties of D‐π‐A azobenzene derivatives by changing the dipole moment and conjugation length: a theoretical study

Tuning the absorption spectra and nonlinear optical properties of D‐π‐A azobenzene derivatives by changing the dipole moment and conjugation length: a theoretical study

Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents

Donor–acceptor diethynylsilane oligomers: A second‐order nonlinear optical material

Contact Info

Product

Resources

About