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. 2021 Oct 20;14(21):6239.
doi: 10.3390/ma14216239.

Alkylated Benzodithienoquinolizinium Salts as Possible Non-Fullerene Organic N-Type Semiconductors: An Experimental and Theoretical Study

Andrés Aracena  1 , Marcos Caroli Rezende  2 , Macarena García  3 , Karina Muñoz-Becerra  4 , Kerry Wrighton-Araneda  5 , Cristian Valdebenito  6 , Freddy Celis  3 , Octavio Vásquez  7
Affiliations

Alkylated Benzodithienoquinolizinium Salts as Possible Non-Fullerene Organic N-Type Semiconductors: An Experimental and Theoretical Study

Andrés Aracena et al. Materials (Basel). .

Abstract

Three photobicyclized benzodithienoquinolizinium tetrafluoroborates (BPDTQBF4) were prepared and evaluated by UV-Vis and fluorescence spectral, electrochemical analysis, and by theoretical calculations as possible organic n-type semiconductors. Evaluation and comparison of their LUMO levels, HOMO-LUMO energy gaps as monomeric and π-stacked dimers with those of other materials, suggest their potential as organic n-type semiconductors. Calculations of their relative charge carrier mobilities confirmed this potential for one derivative with a long (C-14) alkyl chain appended to the polycyclic planar π-system.

Keywords: benzodithienoquinolizinium cations; organic semiconductors; photocyclization of N-aryl pyridinium salts; π-stacked assemblies.

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Conflict of interest statement

There are no conflict to declare.

Figures

Scheme 1
Scheme 1
Synthetic route for the preparation of polycyclic heteroaromatic tetrafluoroborates 4a–c.
Figure 1
Figure 1
UV–Vis spectra of pyridinium tetrafluoroborates 3a–c in chloroform (ca. 9 × 10−4 M).
Figure 2
Figure 2
UV–Vis spectra of photocyclized salts 4a–c (a) in chloroform (ca. 8 × 10−4 M) and (b) in methanol (ca. 8 × 10−4 M).
Figure 3
Figure 3
Fluorescence spectra of photocyclized salts 4a–c (a) in chloroform (ca. 6 × 10−6 M), upon excitation at λmaxexc = 350 nm; (b) in methanol (ca. 8 × 10−6 M), upon excitation at λmaxexc = 350 nm.
Figure 4
Figure 4
Cyclic voltammogram of pyridinium salt 3a (1 mM) in DMF, with 0.1 M TBPA as a supporting electrolyte and a scan rate of 100 mV/s.
Figure 5
Figure 5
Cyclic voltammogram of the BPDTQ tetrafluoroborate 4a (1 mM) in DMF, with 0.1 M TBPA as the supporting electrolyte and a scan rate of 10 V/s.
Figure 6
Figure 6
Thermogravimetric analysis of BPDTQ tetrafluoroborate 4c.
Figure 7
Figure 7
HOMO (a) and LUMO (b) densities of the 4a cation in methanol, calculated using the B3LYP/6-31G(d) method and the PCM option.
Figure 8
Figure 8
Face-to-face (FF) and face-to-tail (FT) alignments of dimers from cations of BPTDQ salt 4a.
Figure 9
Figure 9
Face-to-face (FF) and face-to-tail (FT) π-stacked dimers of cations from 4a–c, with non-covalent interactions obtained from NCI analyses.
Scheme 2
Scheme 2
Hole/electron exchange between two molecules M in a hopping process.
See this image and copyright information in PMC

References

    1. Chen J., Chen Y., Feng L.-W., Gu C., Li G., Su N., Wang G., Swick S.M., Huang W., Guo X., et al. Hole (donor) and electron (acceptor) transporting organic semiconductors for bulk-heterojunction solar cells. EnergyChem. 2020;2:100042. doi: 10.1016/j.enchem.2020.100042. - DOI
    1. Haddon R.C. C 70 Thin Film Transistors. J. Am. Chem. Soc. 1996;118:3041–3042. doi: 10.1021/ja953881w. - DOI
    1. Sugiyama H., Nagano T., Nouchi R., Kawasaki N., Ohta Y., Imai K., Tsutsui M., Kubozono Y., Fujiwara A. Transport properties of field-effect transistors with thin films of C76 and its electronic structure. Chem. Phys. Lett. 2007;449:160–164. doi: 10.1016/j.cplett.2007.10.012. - DOI
    1. Shibata K., Kubozono Y., Kanbara T., Hosokawa T., Fujiwara A., Ito Y., Shinohara H. Fabrication and characteristics of C84 fullerene field-effect transistors. Appl. Phys. Lett. 2004;84:2572–2574. doi: 10.1063/1.1695193. - DOI
    1. Kanbara T., Shibata K., Fujiki S., Kubozono Y., Kashino S., Urisu T., Sakai M., Fujiwara A., Kumashiro R., Tanigaki K. N-channel field effect transistors with fullerene thin films and their application to a logic gate circuit. Chem. Phys. Lett. 2003;379:223–229. doi: 10.1016/j.cplett.2003.07.025. - DOI

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