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. 2017 Mar 6:5:11.
doi: 10.3389/fchem.2017.00011. eCollection 2017.

Computational Studies on Optoelectronic and Nonlinear Properties of Octaphyrin Derivatives

Nasarul Islam  1 , Irfan H Lone  2
Affiliations

Computational Studies on Optoelectronic and Nonlinear Properties of Octaphyrin Derivatives

Nasarul Islam et al. Front Chem. .

Abstract

The electronic and nonlinear optical (NLO) properties of octaphyrin derivatives were studied by employing the DFT/TDFT at CAM-B3LYP/6-311++G (2d, 2p) level of the theory. Thiophene, phenyl, methyl and cyano moieties were substituted on the molecular framework of octaphyrin core, in order to observe the change in optoelectronic and nonlinear response of these systems. The frontier molecular orbital studies and values of electron affinity reveals that the studied compounds are stable against the oxygen and moisture present in air. The calculated ionization energies, adiabatic electron affinity and reorganization energy values indicate that octaphyrin derivatives can be employed as effective n-type material for Organic Light Emitting Diodes (OLEDs). This character shows an enhancement with the introduction of an electron withdrawing group in the octaphyrin framework. The polarizability and hyperpolarizability values of octaphyrin derivatives demonstrate that they are good candidates for NLO devices. The nonlinear response of these systems shows enhancement on the introduction of electron donating groups on octaphyrin moiety. However, these claims needs further experimental verification.

Keywords: bond-length-alternation; hyperpolarizability; mesomeric effect; polarizability; porphyrin; reorganization energy.

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Figures

None
Graphical Abstract.
Figure 1
Figure 1
Sketch of octaphyrin (OP) derivatives study using DFT at CAM-B3LYP/6-311++G (2d, 2p) level of theory.
Figure 2
Figure 2
Optimized geometries of OP derivatives obtained at CAM-B3LYP/6-311++G (2d, 2p) level of calculations.
Figure 3
Figure 3
The frontier molecular orbitals (FMOs) of OP derivatives at DFT/ CAM-B3LYP/6-311++G (2d, 2p) level of theory.
See this image and copyright information in PMC

References

    1. Ahn T. K., Kwon J. H., Kim D. Y., Cho D. W., Jeong D. H., Kim S. K., et al. (2005). Comparative photophysics of [26]- and [28]hexaphyrins(1.1.1.1.1.1): large two-photon absorption cross section of aromatic [26]hexaphyrins(1.1.1.1.1.1). J. Am. Chem. Soc. 127, 12856–12861. 10.1021/ja050895l - DOI - PubMed
    1. Alonso M., Geerlings P., Proft F. D. (2014). Exploring the structure–aromaticity relationship in Hückel and Möbius N-fused pentaphyrins using DFT. Phys. Chem. Chem. Phys. 16, 14396–14407. 10.1039/C3CP55509G - DOI - PubMed
    1. Alonso M., Geerlings P., De Proft F. (2013). Topology switching in [32]heptaphyrins controlled by solvent, protonation, and meso substituents. Chem. Eur. J. 19, 1617–1628. 10.1002/chem.201203295 - DOI - PubMed
    1. Alyar H., Kantarci Z., Bahat M., Kasap E. (2007). Investigation of torsional barriers and nonlinear optical (NLO) properties of phenyltriazines. J. Mol. Struc. 836, 516–520. 10.1016/j.molstruc.2006.11.066 - DOI
    1. Anaka Y., Mori H., Koide T., Yorimitsu H., Aratani N., Osuka A. (2011). Rearrangements of a [36]octaphyrin triggered by nickel(II) metalation: metamorphosis to a directly meso-β-linked diporphyrin. Angew. Chem. Int. Ed. 50, 11460–11464. 10.1002/anie.201105809 - DOI - PubMed

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