Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells
A family of four push–pull porphyrazines of A<sub>3</sub>B type, where each unit A contains two peripheral propyl chains and the unit B is endowed with a carboxylic acid, were prepared. The carboxylic acid was attached to the β-position of the pyrrolic unit, either directly (Pz <b>...
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MDPI AG
2021-04-01
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| Online Access: | https://www.mdpi.com/1420-3049/26/8/2129 |
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| author | Diana-Paola Medina Javier Fernández-Ariza Maxence Urbani Frédéric Sauvage Tomás Torres M. Salomé Rodríguez-Morgade |
| author_facet | Diana-Paola Medina Javier Fernández-Ariza Maxence Urbani Frédéric Sauvage Tomás Torres M. Salomé Rodríguez-Morgade |
| author_sort | Diana-Paola Medina |
| collection | DOAJ |
| description | A family of four push–pull porphyrazines of A<sub>3</sub>B type, where each unit A contains two peripheral propyl chains and the unit B is endowed with a carboxylic acid, were prepared. The carboxylic acid was attached to the β-position of the pyrrolic unit, either directly (Pz <b>10</b>), or through cyanovinyl (Pz <b>11</b>) and phenyl (Pz <b>7</b>) groups. The fourth Pz (<b>14</b>) consisted in a pyrazinoporphyrazine wherein the dinitrogenated heterocycle provided intrinsic donor–acceptor character to the macrocycle and contained a carboxyphenyl substituent. The direct attachment of the carboxylic acid functions and their linkers to the porphyrazine core produces stronger perturbation on the electronic properties of the macrocycle, with respect to their connection through fused benzene or pyrazine rings in <b>TT112</b> and <b>14</b>, respectively. The HOMO and LUMO energies of the Pzs, which were estimated with DFT calculations, show little variation within the series, except upon introduction of the cyanovinyl spacer, which produces a decrease in both frontier orbital energetic levels. This effective interaction of cyanovinyl substitution with the macrocycle is also evidenced in UV/Vis spectroscopy, where a large splitting of the Q-band indicates strong desymmetrization of the Pz. The performance of the four Pzs as photosensitizers in DSSCs were also investigated. |
| first_indexed | 2024-03-10T12:31:36Z |
| format | Article |
| id | doaj.art-1d92771bfd3b4a55852d72985f7c290d |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T12:31:36Z |
| publishDate | 2021-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-1d92771bfd3b4a55852d72985f7c290d2023-11-21T14:35:19ZengMDPI AGMolecules1420-30492021-04-01268212910.3390/molecules26082129Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar CellsDiana-Paola Medina0Javier Fernández-Ariza1Maxence Urbani2Frédéric Sauvage3Tomás Torres4M. Salomé Rodríguez-Morgade5Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, SpainDepartamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, SpainInstituto Madrileño de Estudios Avanzados (IMDEA)-Nanociencia, c/ Faraday, 9, Cantoblanco, 28049 Madrid, SpainLaboratoire de Réactivité et Chimie des Solides, Université de Picardie Jules Verne, CNRS UMR7314, Hub de L’énergie, 15 rue Baudelocque, 80039 Amiens, FranceDepartamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, SpainDepartamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, SpainA family of four push–pull porphyrazines of A<sub>3</sub>B type, where each unit A contains two peripheral propyl chains and the unit B is endowed with a carboxylic acid, were prepared. The carboxylic acid was attached to the β-position of the pyrrolic unit, either directly (Pz <b>10</b>), or through cyanovinyl (Pz <b>11</b>) and phenyl (Pz <b>7</b>) groups. The fourth Pz (<b>14</b>) consisted in a pyrazinoporphyrazine wherein the dinitrogenated heterocycle provided intrinsic donor–acceptor character to the macrocycle and contained a carboxyphenyl substituent. The direct attachment of the carboxylic acid functions and their linkers to the porphyrazine core produces stronger perturbation on the electronic properties of the macrocycle, with respect to their connection through fused benzene or pyrazine rings in <b>TT112</b> and <b>14</b>, respectively. The HOMO and LUMO energies of the Pzs, which were estimated with DFT calculations, show little variation within the series, except upon introduction of the cyanovinyl spacer, which produces a decrease in both frontier orbital energetic levels. This effective interaction of cyanovinyl substitution with the macrocycle is also evidenced in UV/Vis spectroscopy, where a large splitting of the Q-band indicates strong desymmetrization of the Pz. The performance of the four Pzs as photosensitizers in DSSCs were also investigated.https://www.mdpi.com/1420-3049/26/8/2129porphyrazinespush–pull systemsamphiphilic systemsdye-sensitized solar cellsphotovoltaics |
| spellingShingle | Diana-Paola Medina Javier Fernández-Ariza Maxence Urbani Frédéric Sauvage Tomás Torres M. Salomé Rodríguez-Morgade Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells Molecules porphyrazines push–pull systems amphiphilic systems dye-sensitized solar cells photovoltaics |
| title | Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells |
| title_full | Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells |
| title_fullStr | Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells |
| title_full_unstemmed | Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells |
| title_short | Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells |
| title_sort | tuning the acceptor unit of push pull porphyrazines for dye sensitized solar cells |
| topic | porphyrazines push–pull systems amphiphilic systems dye-sensitized solar cells photovoltaics |
| url | https://www.mdpi.com/1420-3049/26/8/2129 |
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