{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,10]],"date-time":"2026-03-10T01:22:59Z","timestamp":1773105779699,"version":"3.50.1"},"reference-count":25,"publisher":"MDPI AG","issue":"24","license":[{"start":{"date-parts":[[2019,12,5]],"date-time":"2019-12-05T00:00:00Z","timestamp":1575504000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>In the present work, five 2-styryl-1-benzopyrylium salts and their relative self-assembly processes towards TiO2 nanocrystalline layers were evaluated as photosensitizers in dye-sensitized solar cells (DSSCs). Integration of these 2-styryl-1-benzopyrylium salts with the semiconductor allow for the performance of highly specific functions suitable for smart applications in material science. Spectroscopic and photoelectrochemical measurements conducted on these five bio-inspired dyes, in solution and upon adsorption onto titanium dioxide films, allowed detailed discussion of the anchoring ability of the different donor groups decorating the 2-styryl-1-benzopyrylium core and have demonstrated their ability as photosensitizers. Our results suggest that the introduction of a dimethylamino group in position 4\u2032 of the 2-styryl-1-benzopyrylium skeleton can alter the conjugation of the molecule leading to larger absorption in the visible region and a stronger electron injection of the dye into the conduction band of TiO2. Moreover, our experimental data have been supported by theoretical calculations with the aim to study the energy of the excited states of the five compounds. In this specific case, the simulations reported contributed to better describe the properties of the compounds used and to help create the necessary basis for the design of new and targeted bio-inspired molecules.<\/jats:p>","DOI":"10.3390\/ma12244060","type":"journal-article","created":{"date-parts":[[2019,12,5]],"date-time":"2019-12-05T11:16:23Z","timestamp":1575544583000},"page":"4060","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["A Photoelectrochemical Study of Bioinspired 2-Styryl-1-Benzopyrylium Cations on TiO2 Nanoparticle Layer for Application in Dye-Sensitized Solar Cells"],"prefix":"10.3390","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0409-1440","authenticated-orcid":false,"given":"Giuseppe","family":"Calogero","sequence":"first","affiliation":[{"name":"CNR-IPCF, Viale Ferdinando Stagno d\u2019Alcontres 37, 98158 Messina, Italy"}]},{"given":"Ilaria","family":"Citro","sequence":"additional","affiliation":[{"name":"CNR-IPCF, Viale Ferdinando Stagno d\u2019Alcontres 37, 98158 Messina, Italy"}]},{"given":"Gioacchino","family":"Calandra Sebastianella","sequence":"additional","affiliation":[{"name":"CNR-IPCF, Viale Ferdinando Stagno d\u2019Alcontres 37, 98158 Messina, Italy"},{"name":"Department of Biomedical, Metabolic and Neural Sciences, University Modena e Reggio Emilia, Via Campi 287, 41121 Modena, Italy"}]},{"given":"Gaetano","family":"Di Marco","sequence":"additional","affiliation":[{"name":"CNR-IPCF, Viale Ferdinando Stagno d\u2019Alcontres 37, 98158 Messina, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3157-6937","authenticated-orcid":false,"given":"Ana Marta","family":"Diniz","sequence":"additional","affiliation":[{"name":"Health Technology College of Lisbon (ESTeSL)\u2014Polytechnic Institute of Lisbon, 1990-096 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1333-9076","authenticated-orcid":false,"given":"A. Jorge","family":"Parola","sequence":"additional","affiliation":[{"name":"LAQV-REQUIMTE, Departamento de Qu\u00edmica, Universidade NOVA de Lisboa, 2829-516 Monte de Caparica, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8529-6848","authenticated-orcid":false,"given":"Fernando","family":"Pina","sequence":"additional","affiliation":[{"name":"LAQV-REQUIMTE, Departamento de Qu\u00edmica, Universidade NOVA de Lisboa, 2829-516 Monte de Caparica, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2019,12,5]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"609","DOI":"10.1016\/j.colsurfb.2018.06.031","article-title":"Soft nanoparticles charge expression within lipid membranes: The case of amino terminated dendrimers in bilayers vesicles","volume":"170","author":"Lombardo","year":"2018","journal-title":"Colloids Surf. B Biointerfaces"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"11983","DOI":"10.1039\/C9CP02195G","article-title":"Evidence of pre-micellar aggregates in aqueous solution of amphiphilic PDMS\u2013PEO block copolymer","volume":"21","author":"Lombardo","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/j.micromeso.2012.10.024","article-title":"Growth of fractal aggregates during template directed SAPO-34 zeolite formation","volume":"167","author":"Bonaccorsi","year":"2013","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"7079","DOI":"10.1021\/la400951s","article-title":"Self-assembly in poly (dimethylsiloxane)\u2013poly (ethylene oxide) block copolymer template directed synthesis of Linde type A zeolite","volume":"29","author":"Bonaccorsi","year":"2013","journal-title":"Langmuir"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"141","DOI":"10.25088\/ComplexSystems.20.2.141","article-title":"Systematic Prediction of Dyes for Dye-Sensitized Solar Cells: Data Mining via Molecular Charge-Transfer Algorithms","volume":"20","author":"Cole","year":"2011","journal-title":"Complex Syst."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1802820","DOI":"10.1002\/aenm.201802820","article-title":"Design-to-Device Approach Affords Panchromatic Co-Sensitized Solar Cells","volume":"9","author":"Cooper","year":"2018","journal-title":"Adv. Energy Mater."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"869","DOI":"10.1039\/C1CS15126F","article-title":"Chemistry and Applications of Flavylium Compounds: A Handful of Colours","volume":"41","author":"Pina","year":"2012","journal-title":"Chem. Soc. Rev."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/j.optmat.2018.11.005","article-title":"Absorption spectra, thermal analysis, photoelectrochemical characterization and stability test of vegetable-based dye-sensitized solar cells","volume":"88","author":"Calogero","year":"2019","journal-title":"Opt. Mater."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"3244","DOI":"10.1039\/C4CS00309H","article-title":"Vegetable-based Dye-Sensitized Solar Cells","volume":"44","author":"Calogero","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"883","DOI":"10.1039\/c3pp25347c","article-title":"Synthetic analogues of anthocyanins as sensitizers for dye-sensitized solar cells","volume":"12","author":"Calogero","year":"2013","journal-title":"Photochem. Photobiol. Sci."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1400","DOI":"10.1039\/c7pp00039a","article-title":"Electronic and charge transfer properties of bio-inspired flavylium ions for applications to TiO2-based dye-sensitized solar cells","volume":"16","author":"Calogero","year":"2017","journal-title":"Photochem. Photobiol. Sci."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"100","DOI":"10.1016\/j.solener.2019.08.050","article-title":"Study of the multi-equilibria of red wine colorants pyranoanthocyanins and evaluation of their potential in dye-sensitized solar cells","volume":"191","author":"Pinto","year":"2019","journal-title":"Sol. Energy"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"107577","DOI":"10.1016\/j.dyepig.2019.107577","article-title":"Catechol versus carboxyl linkage impact on DSSC performance of synthetic pyranoflavylium salts","volume":"170","author":"Pinto","year":"2019","journal-title":"Dyes Pigment."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"69","DOI":"10.1016\/j.dyepig.2008.09.007","article-title":"The synthesis and reaction network of 2-styryl-1-benzopyrylium salts: An unexploited class of potential colorants","volume":"81","author":"Gomes","year":"2009","journal-title":"Dyes Pigment."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"719","DOI":"10.1021\/jp807024d","article-title":"Photochemistry of 7-hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium and related compounds","volume":"113","author":"Diniz","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"8107","DOI":"10.1021\/jp303589n","article-title":"Isomerisation Between 2-(2,4-Dihydroxystyryl)-1-benzopyrylium and 7-Hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium","volume":"116","author":"Petrov","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_17","first-page":"1933","article-title":"Experimental and theoretical study of the styrylbenzopyrylium chromophore","volume":"11","year":"1992","journal-title":"J. Chem. Soc. Perkin Trans. 2"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-functional thermochemistry. III. The role of exact exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"11100","DOI":"10.1021\/jp074941a","article-title":"A Density Functional Theory Study on Pelargonidin","volume":"111","author":"Mosquera","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"15118","DOI":"10.1021\/jp9052538","article-title":"Absorption and Emission of the Apigenin and Luteolin Flavonoids: A TDDFT Investigation","volume":"113","author":"Amat","year":"2009","journal-title":"J. Phys. Chem. A"},{"key":"ref_22","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Vreven, T., Kudin, K.N., and Burant, J.C. (2004). Gaussian 03, Revision C.02, Gaussian, Inc."},{"key":"ref_23","unstructured":"Mataga, N., and Kubota, T. (1970). Molecular Interactions and Electronic Spectra, Marcel Dekker, Inc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"8922","DOI":"10.1021\/ja9019098","article-title":"Host-guest interactions between molecular clips and multistate systems based on flavylium salts","volume":"131","author":"Gomes","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"9342","DOI":"10.1021\/jp972197w","article-title":"Ultrafast Electron Injection: Implications for a Photoelectrochemical Cell Utilizing an Anthocyanin Dye-Sensitized TiO2 Nanocrystalline Electrode","volume":"101","author":"Cherepy","year":"1997","journal-title":"J. Phys. Chem. B"}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/12\/24\/4060\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T13:40:31Z","timestamp":1760190031000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/12\/24\/4060"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,12,5]]},"references-count":25,"journal-issue":{"issue":"24","published-online":{"date-parts":[[2019,12]]}},"alternative-id":["ma12244060"],"URL":"https:\/\/doi.org\/10.3390\/ma12244060","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,12,5]]}}}