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Insighting the systematic impact of shape, size and substitution of heteroatoms in quinoidal oligomers to tune their optoelectronic properties

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Abstract

In the present investigation, a variety of quinoidal oligomers with different arrangements and distinctive fused shapes of thiophene rings are studied. These quinoidal oligomers were further explored for the systematic heteroatom substitution using state-of-art quantum computational methods. The substitution of S atoms by O and N in oligomer compounds is done to see change in optical and nonlinear optical properties while moving from series 1 to series 4. The substitution of oligomer chain shows a significant effect on linear polarizability, first and second hyperpolarizabilities as calculated at M06/6-311G** level of theory. All the studied compounds showed relatively average first hyperpolarizability while reasonably large second hyperpolarizability. Among all the studied compounds, the largest second hyperpolarizability of 1003 × 10–36 esu is shown by 4c which is ~ 138 times greater than standard p-NA molecule. Interestingly, TD-DFT analysis indicates that the series 4 has larger oscillator strengths and lower transition energy values which contributes to its enlarged amplitude of second hyperpolarizability response. Furthermore, the transition density matrix, frontier molecular orbitals and molecular electrostatic potential diagrams showed that the charge transfer occurs from oligomer chain to cyanide groups and this charge transfer is highly dependent on the substitution patterns. The density of states diagrams of the selected class of compounds 4a, 4b and 4c show that 4c has significant partial contributions of oligomer chain in HOMO–LUMO orbitals. Thus, the comparative study of four series of compounds indicates not only the importance of shape and size of oligomer molecules but also indicates the importance of heteroatom substitutions to attain a vigorous second hyperpolarizability response for their potential use in optoelectronic and NLO applications.

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The optimized coordinates required to produce these findings are given in supporting information.

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Acknowledgements

The authors extend their appreciation to Deanship of Scientific Research at King Khalid University for funding the work through Large Groups Project under grant number (RGP.2/194/43). This research was also supported by the KU Brain Pool 2021 of Konkuk University, Seoul, South Korea.

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Authors and Affiliations

  1. Department of Chemistry, University of Agriculture, Faisalabad, 38000, Pakistan

    Fatima Sarwar,  Shafiq‐urRehman & Shamsa Bibi

  2. Department of Chemistry, College of Science, King Khalid University, P.O. Box 9004, Abha, 61413, Saudi Arabia

    Shabbir Muhammad & Abdullah G. Al-Sehemi

  3. Department of Physics, College of Science, King Khalid University, P.O. Box 9004, Abha, 61413, Saudi Arabia

    H. Algarni

  4. Division of Chemical Engineering, Konkuk University, Seoul, 05029, Republic of Korea

    Santosh Kumar

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  1. Fatima Sarwar
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  2. Shabbir Muhammad
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  3. Shafiq‐urRehman
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  4. Shamsa Bibi
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  5. Abdullah G. Al-Sehemi
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Contributions

FS has written the methodology and discussion, visualization. SM has considered the idea and performed calculations. SR has performed conceptualization and technical supervision SB has done supervision and formal analysis of results SK has done project administration and funding acquisition, AGA and HA have provided technical support and writing methodology and Supervision.

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Correspondence to Shabbir Muhammad, Shafiq‐urRehman or Shamsa Bibi.

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Sarwar, F., Muhammad, S., Shafiq‐urRehman et al. Insighting the systematic impact of shape, size and substitution of heteroatoms in quinoidal oligomers to tune their optoelectronic properties. Opt Quant Electron 54, 356 (2022). https://doi.org/10.1007/s11082-022-03724-6

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