Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2020 Mar 12;10(18):10569-10576.
doi: 10.1039/d0ra00610f. eCollection 2020 Mar 11.

Design of high performance p-type sensitizers with pyridinium derivatives as the acceptor by theoretical calculations

Zhi-Dan Sun  1 , Jiang-Shan Zhao  1 , Karuppasamy Ayyanar  1 , Xue-Hai Ju  1 , Qi-Ying Xia  2
Affiliations

Design of high performance p-type sensitizers with pyridinium derivatives as the acceptor by theoretical calculations

Zhi-Dan Sun et al. RSC Adv. .

Abstract

Based on triphenylamine as an electron donor and thiophene as a π-linker, Series P and A p-type sensitizers were designed to investigate the effects of the different acceptors on the properties of the sensitizers. The optimized molecular structures, electronic and optical properties were investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT). The results showed that the properties of the dyes can be tuned by the introduction of the different electron-withdrawing groups to the N atom in the pyridinium acceptor. Compared with the synthesized Series P dyes used in p-type sensitizers, the properties of Series A dyes, except for two dyes that cannot be used as p-type sensitizers, are improved by means of modifying pyridinium acceptors. Due to the suitable electron-withdrawing ability of the hexafluorodiacetylamino group in its acceptor, A6 has the narrowest energy gap (1.90 eV), the largest driving force of hole injection (ΔG inj, -0.68 eV), the high light harvesting efficiency (LHE, 0.9984) and the smallest internal reorganization energy (λ int, 5.05 kcal mol-1). Hence, A6 not only enhances electronic excitation, but also improves the reorganization energy. Importantly, A6 shows the largest red shift and the maximum integral values of the adsorption over the visible light, as well as the strongest adsorption energy (-74.80 kcal mol-1) on a NiO surface. Thus, A6 may be a promising sensitizer for the p-type dye-sensitized solar cells (DSSCs), and the acceptor of A6 may provide a new and easily accessible high performance acceptor for p-type sensitizers.

PubMed Disclaimer

Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Molecular structures of the investigated dyes.
Fig. 2
Fig. 2. Frontier molecular orbital energy levels and energy gap, together with EVB (NiO) and E(I3−/I2˙−).
Fig. 3
Fig. 3. Absorption spectra for Series P dyes (a), Series A with cyclic ketone groups (b), Series A with ester or aliphatic ketone groups (c) and overall dyes (d) at CAM-B3LYP/6-311G** level.
Fig. 4
Fig. 4. The integral area of absorption–wavelength curve over 400–800 nm.
Fig. 5
Fig. 5. The front view (a) and lateral view (b) of the optimized dye/(NiO)12×3 structures for P1 and A6.
See this image and copyright information in PMC

References

    1. O'Regan B. Grätzel M. Nature. 1991;353:737–740. doi: 10.1038/353737a0. - DOI
    1. Kakiage K. Aoyama Y. Yano T. Oya K. Fujisawa J. I. Hanaya M. Chem. Commun. 2015;51:15894–15897. doi: 10.1039/C5CC06759F. - DOI - PubMed
    1. Perera I. R. Daeneke T. Makuta S. Yu Z. Tachibana Y. Mishra A. Bäuerle P. Ohlin C. A. Bach U. Spiccia L. Angew. Chem., Int. Ed. 2015;54:3758–3762. doi: 10.1002/anie.201409877. - DOI - PubMed
    1. Jing X. Y. Sun l. B. Li D. Y. Wang C. L. Bai F. Q. RSC Adv. 2018;8:29917–29923. doi: 10.1039/C8RA04450C. - DOI - PMC - PubMed
    1. Kong L. X. He M. F. Yan W. Zhang C. S. Ju X. H. J. Chin. Chem. Soc. 2019:1–6.