Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical Modeling
A series of <b>PFDPP</b> copolymers based on fluorene (F) and diketopyrrolopyrrole (DPP) monomers were synthesized via direct arylation polycondensation using Fagnou conditions which involved palladium acetate as catalyst (a gradual catalyst addition of three different percentages were u...
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MDPI AG
2022-05-01
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| Series: | Energies |
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| Online Access: | https://www.mdpi.com/1996-1073/15/11/3855 |
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| author | Jonatan Rodríguez-Rea Marisol Güizado-Rodríguez José-Luis Maldonado Gabriel Ramos-Ortiz José Ulises Reveles Carlos Silva Victor Barba Esmeralda Monserrat Saucedo-Salazar María Teresa Rodríguez Hernández |
| author_facet | Jonatan Rodríguez-Rea Marisol Güizado-Rodríguez José-Luis Maldonado Gabriel Ramos-Ortiz José Ulises Reveles Carlos Silva Victor Barba Esmeralda Monserrat Saucedo-Salazar María Teresa Rodríguez Hernández |
| author_sort | Jonatan Rodríguez-Rea |
| collection | DOAJ |
| description | A series of <b>PFDPP</b> copolymers based on fluorene (F) and diketopyrrolopyrrole (DPP) monomers were synthesized via direct arylation polycondensation using Fagnou conditions which involved palladium acetate as catalyst (a gradual catalyst addition of three different percentages were used), potassium carbonate as the base, and neodecanoic acid in <i>N</i>, <i>N</i>-dimethylacetamide. This synthesis provides a low cost compared with traditional methods of transition-metal-catalyzed polymerization. Among the different amounts of catalyst used in the present work, 12% was optimal because it gave the highest reaction yield (81.5%) and one of the highest molecular weights (Mn = 13.8 KDa). Copolymers’ chemical structures, molecular weight distributions, and optical and thermal properties were analyzed. The linear optical properties of <b>PFDPP</b> copolymers resulted very similarly independently to the catalyst amounts used in the synthesis of the <b>PFDPP</b> copolymers: two absorptions bands distinctive of donor–acceptor copolymers, Stokes shifts of 41 nm, a good quantum yield of fluorescence around 47%, and an optical bandgap of 1.7 eV were determined. Electronic nonlinearities were observed in these copolymers with a relatively high two-photon absorption cross-section of 621 GM at 950 nm. The dynamics of excited states and aggregation effects were studied in solutions, nanoparticles, and films of <b>PFDPP</b>. Theoretical calculations modeled the ground-state structures of the (<b>PFDPP</b>)<sub>n</sub> copolymers with n = 1 to 4 units, determining the charge distribution by the electrostatic potential and modeling the absorption spectra determining the orbital transitions responsible for the experimentally observed leading bands. Experimental and theoretical structure–properties analysis of these donor–acceptor copolymers allowed finding their best synthesis conditions to use them in optoelectronic applications. |
| first_indexed | 2024-03-10T01:23:29Z |
| format | Article |
| id | doaj.art-fefb8f2de2174e1fbc6ba0a5496fe840 |
| institution | Directory Open Access Journal |
| issn | 1996-1073 |
| language | English |
| last_indexed | 2024-03-10T01:23:29Z |
| publishDate | 2022-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Energies |
| spelling | doaj.art-fefb8f2de2174e1fbc6ba0a5496fe8402023-11-23T13:56:17ZengMDPI AGEnergies1996-10732022-05-011511385510.3390/en15113855Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical ModelingJonatan Rodríguez-Rea0Marisol Güizado-Rodríguez1José-Luis Maldonado2Gabriel Ramos-Ortiz3José Ulises Reveles4Carlos Silva5Victor Barba6Esmeralda Monserrat Saucedo-Salazar7María Teresa Rodríguez Hernández8Centro de Investigación en Ingeniería y Ciencias Aplicadas (CIICAp)-IICBA, Universidad Autónoma del Estado de Morelos (UAEM), Av. Universidad No. 1001, Col. Chamilpa, Cuernavaca C.P. 62209, MexicoCentro de Investigación en Ingeniería y Ciencias Aplicadas (CIICAp)-IICBA, Universidad Autónoma del Estado de Morelos (UAEM), Av. Universidad No. 1001, Col. Chamilpa, Cuernavaca C.P. 62209, MexicoCentro de Investigaciones en Óptica A.C., Loma del Bosque No. 115, Col. Lomas del Campestre, Leon C.P. 37150, MexicoCentro de Investigaciones en Óptica A.C., Loma del Bosque No. 115, Col. Lomas del Campestre, Leon C.P. 37150, MexicoCristo Rey Richmond High School, 313 N Belmont Ave, Richmond, VA 23221, USASchool of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Drive NW, Atlanta, GA 30332, USACentro de Investigaciones Químicas (CIQ)-IICBA, Universidad Autónoma del Estado de Morelos (UAEM), Av. Universidad No. 1001, Col. Chamilpa, Cuernavaca C.P. 62209, MexicoLaboratorio Central de Instrumentación Analítica, Centro de Investigación en Química Aplicada (CIQA), Blvd. Enrique Reyna Hermosillo No. 140 Saltillo, Saltillo C.P. 25294, MexicoLaboratorio Central de Instrumentación Analítica, Centro de Investigación en Química Aplicada (CIQA), Blvd. Enrique Reyna Hermosillo No. 140 Saltillo, Saltillo C.P. 25294, MexicoA series of <b>PFDPP</b> copolymers based on fluorene (F) and diketopyrrolopyrrole (DPP) monomers were synthesized via direct arylation polycondensation using Fagnou conditions which involved palladium acetate as catalyst (a gradual catalyst addition of three different percentages were used), potassium carbonate as the base, and neodecanoic acid in <i>N</i>, <i>N</i>-dimethylacetamide. This synthesis provides a low cost compared with traditional methods of transition-metal-catalyzed polymerization. Among the different amounts of catalyst used in the present work, 12% was optimal because it gave the highest reaction yield (81.5%) and one of the highest molecular weights (Mn = 13.8 KDa). Copolymers’ chemical structures, molecular weight distributions, and optical and thermal properties were analyzed. The linear optical properties of <b>PFDPP</b> copolymers resulted very similarly independently to the catalyst amounts used in the synthesis of the <b>PFDPP</b> copolymers: two absorptions bands distinctive of donor–acceptor copolymers, Stokes shifts of 41 nm, a good quantum yield of fluorescence around 47%, and an optical bandgap of 1.7 eV were determined. Electronic nonlinearities were observed in these copolymers with a relatively high two-photon absorption cross-section of 621 GM at 950 nm. The dynamics of excited states and aggregation effects were studied in solutions, nanoparticles, and films of <b>PFDPP</b>. Theoretical calculations modeled the ground-state structures of the (<b>PFDPP</b>)<sub>n</sub> copolymers with n = 1 to 4 units, determining the charge distribution by the electrostatic potential and modeling the absorption spectra determining the orbital transitions responsible for the experimentally observed leading bands. Experimental and theoretical structure–properties analysis of these donor–acceptor copolymers allowed finding their best synthesis conditions to use them in optoelectronic applications.https://www.mdpi.com/1996-1073/15/11/3855diketopyrrolopyrroledirect arylation polymerizationfluorenephotophysical properties |
| spellingShingle | Jonatan Rodríguez-Rea Marisol Güizado-Rodríguez José-Luis Maldonado Gabriel Ramos-Ortiz José Ulises Reveles Carlos Silva Victor Barba Esmeralda Monserrat Saucedo-Salazar María Teresa Rodríguez Hernández Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical Modeling Energies diketopyrrolopyrrole direct arylation polymerization fluorene photophysical properties |
| title | Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical Modeling |
| title_full | Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical Modeling |
| title_fullStr | Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical Modeling |
| title_full_unstemmed | Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical Modeling |
| title_short | Synthesis of Donor–Acceptor Copolymers Derived from Diketopyrrolopyrrole and Fluorene via Eco-Friendly Direct Arylation: Nonlinear Optical Properties, Transient Absorption Spectroscopy, and Theoretical Modeling |
| title_sort | synthesis of donor acceptor copolymers derived from diketopyrrolopyrrole and fluorene via eco friendly direct arylation nonlinear optical properties transient absorption spectroscopy and theoretical modeling |
| topic | diketopyrrolopyrrole direct arylation polymerization fluorene photophysical properties |
| url | https://www.mdpi.com/1996-1073/15/11/3855 |
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