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. 2014 Dec 5;9(12):e114125.
doi: 10.1371/journal.pone.0114125. eCollection 2014.

Electron transport and nonlinear optical properties of substituted aryldimesityl boranes: a DFT study

Altaf Hussain Pandith  1 , Nasarul Islam  1
Affiliations

Electron transport and nonlinear optical properties of substituted aryldimesityl boranes: a DFT study

Altaf Hussain Pandith et al. PLoS One. .

Abstract

A comprehensive theoretical study was carried out on a series of aryldimesityl borane (DMB) derivatives using Density Functional theory. Optimized geometries and electronic parameters like electron affinity, reorganization energy, frontiers molecular contours, polarizability and hyperpolarizability have been calculated by employing B3PW91/6-311++G (d, p) level of theory. Our results show that the Hammett function and geometrical parameters correlates well with the reorganization energies and hyperpolarizability for the series of DMB derivatives studied in this work. The orbital energy study reveals that the electron releasing substituents increase the LUMO energies and electron withdrawing substituents decrease the LUMO energies, reflecting the electron transport character of aryldimesityl borane derivatives. From frontier molecular orbitals diagram it is evident that mesityl rings act as the donor, while the phenylene and Boron atom appear as acceptors in these systems. The calculated hyperpolarizability of secondary amine derivative of DMB is 40 times higher than DMB (1). The electronic excitation contributions to the hyperpolarizability studied by using TDDFT calculation shows that hyperpolarizability correlates well with dipole moment in ground and excited state and excitation energy in terms of the two-level model. Thus the results of these calculations can be helpful in designing the DMB derivatives for efficient electron transport and nonlinear optical material by appropriate substitution with electron releasing or withdrawing substituents on phenyl ring of DMB system.

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Conflict of interest statement

Competing Interests: The authors have declared that no competing interests exist.

Figures

Figure 1
Figure 1. Sketch of aryldimesityl borane (DMB) derivatives study using DFT at B3PW91/6-311++G (d,p)level of theory.
Figure 2
Figure 2. Plot of geometrical change (dihedral angle) with the Hammett Parameter, for the series of studied DMB derivates.
Figure 3
Figure 3. Calculation details of the reorganization energy (eV) for the electron transport, λ1 is reorganization energy of a neutral molecule and λ2 reorganization energy of a anionic-radical.
Figure 4
Figure 4. Plot of reorganization energy (eV) with Hammett parameter of (a) DMB derivatives with electron releasing substituents, (b) DMB derivatives with electron withdrawing substituents.
Figure 5
Figure 5. Calculated HOMO energies, LUMO energies of DMB derivatives (a) electron releasing substituents, (b) electron withdrawing substituents, together with the LUMO-HOMO gap at DFT/B3PW91/6-311++G (d,p) level of theory.
Figure 6
Figure 6. Plot of Hammett Parameter with (a) electron affinity (eV) and (b) ionization potential (eV).
Figure 7
Figure 7. The frontier molecular orbitals (FMOs) of DMB derivatives at DFT/B3PW91/6-311G (d,p)++ level of theory.
Figure 8
Figure 8. Schematic diagram of a two-layered OLED device.
Figure 9
Figure 9. Plot of Hammett parameter with hyperpolarizability (10−30 esu) of (a) DMB derivative with electron releasing group and (b) DMB derivates with electron withdrawing groups.
See this image and copyright information in PMC

References

    1. Garcia G, Garzon A, Granadino-Roldan JM, Moral M, Navarro A (2011) Fernandez-Gomez, M. Optoelectronic and charge transport properties of oligomers based on phenylethynylene units linked to thioene-acenes: A DFT study. J Phys Chem C 115:6922–5932.
    1. Glogowski ME, Williams JLR (1981) Boron Photochemistry: XV. Determination of the hammett substituent constant for the p-dimesitylborylgroup. J Organomet Chem 218: 137-146. (b) Grisdale PJ, Williams JLR, Glogowski ME, Babb BE (1971) Boron photochemistry. Possible role of bridged intermediates in the photolysis of borate complexes. J Org Chem 36:544–549.
    1. Entwistle CD, Marder TB (2004) Applications of three-coordinate organoboron compounds and polymers in optoelectronics, special issue on organic electronics. Chem Mater 16:4574–4585.
    1. Jäkle F (2006) Lewis-Acidic Boron Polymers. Coord Chem Rev 250:1107–1121.
    1. Entwistle CD, Marder TB (2002) Boron Chemistry Lights the Way: Optical Properties of Molecular and Polymeric Systems. Angew Chem Int Ed Engl41: 2927–2931; (2002) Angew Chem 114: 3051–3056. - PubMed

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