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.
Highlights
A great deal of interest has recently been aroused in organic materials for their active role in opto-electronic devices such as photovoltaic cells and organic lightemitting diodes (OLEDs) [1]
One important observation is that the highest occupied molecular orbitals (HOMOs)-lowest unoccupied molecular orbitals (LUMOs) gap, DE(H-L), of the studied compounds decrease as compared to un-substituted DMB and this gap goes on decreasing with increase in the electron donating as well as electron withdrawing character of the substituents
The geometrical parameters optimized at B3PW91/6-311++G (d, p) level are in agreement with the experimental ones
Summary
A great deal of interest has recently been aroused in organic materials for their active role in opto-electronic devices such as photovoltaic cells and organic lightemitting diodes (OLEDs) [1]. The calculated reorganization energies for electron transport l1, l2 and li are shown in Table 2 From Table 2, it is clear that the value of li decrease both for DMB derivatives with electron releasing (2–7) and electron withdrawing (7–13) substituents as compared to non-substituted DMB (1), with exception of compound 8 and 9, where it slightly increases.
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