Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials
In this research, we investigated the second-order nonlinear optical (NLO) properties of multicomponent hybrid materials formed by <i>meso</i>-tetraphenylporphyrin P (both as free base and Zn<sup>II</sup> complex), carrying in 2 or 2,12 β-pyrrolic position an electron donor f...
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MDPI AG
2021-08-01
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| Online Access: | https://www.mdpi.com/1996-1944/14/16/4404 |
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| author | Francesca Limosani Francesca Tessore Gabriele Di Carlo Alessandra Forni Pietro Tagliatesta |
| author_facet | Francesca Limosani Francesca Tessore Gabriele Di Carlo Alessandra Forni Pietro Tagliatesta |
| author_sort | Francesca Limosani |
| collection | DOAJ |
| description | In this research, we investigated the second-order nonlinear optical (NLO) properties of multicomponent hybrid materials formed by <i>meso</i>-tetraphenylporphyrin P (both as free base and Zn<sup>II</sup> complex), carrying in 2 or 2,12 β-pyrrolic position an electron donor ferrocene (Fc), and/or an electron acceptor fullerene (C60) moiety, connected to the porphyrin core via an ethynyl or an ethynylphenyl spacer. We measured the NLO response by the electric-field-induced second-harmonic generation (EFISH) technique in CH<sub>2</sub>Cl<sub>2</sub> solution with a 1907 nm incident wavelength, recording for all the investigated compounds unexpected negative values of μβ<sub>1907</sub>. Since density functional theory (DFT) calculations evidenced for P-Fc dyads almost null ground state dipole moments and very low values for P-C60 dyads and Fc-P-C60 triads, our EFISH results suggested a significant contribution to γ<sub>EFISH</sub> of the purely electronic cubic term γ(−2ω; ω, ω, 0), which prevails on the quadratic dipolar orientational one μβ(−2ω; ω, ω)/5kT, as confirmed by computational evidence. |
| first_indexed | 2024-03-10T08:39:24Z |
| format | Article |
| id | doaj.art-bffcd3fb398646509e1349db867b5bf1 |
| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-03-10T08:39:24Z |
| publishDate | 2021-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Materials |
| spelling | doaj.art-bffcd3fb398646509e1349db867b5bf12023-11-22T08:27:04ZengMDPI AGMaterials1996-19442021-08-011416440410.3390/ma14164404Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid MaterialsFrancesca Limosani0Francesca Tessore1Gabriele Di Carlo2Alessandra Forni3Pietro Tagliatesta4Photonics Micro and Nanostructures Laboratory, Physical Technologies for Safety and Health Division, Fusion and Technologies for Nuclear Safety and Security Department, ENEA C.R. Frascati, Via E. Fermi 45, 00044 Frascati, Rome, ItalyDepartment of Chemistry, University of Milan, INSTM Research Unit, Via C. Golgi 19, 20133 Milan, ItalyDepartment of Chemistry, University of Milan, INSTM Research Unit, Via C. Golgi 19, 20133 Milan, ItalyCNR-SCITEC, Istituto di Scienze e Tecnologie Chimiche “G. Natta”, c/o University of Milan, Via Golgi 19, 20133 Milan, ItalyDepartment of Chemical Science and Technologies, University of Rome “Tor Vergata”, Via della Ricerca Scientifica 1, 00133 Rome, ItalyIn this research, we investigated the second-order nonlinear optical (NLO) properties of multicomponent hybrid materials formed by <i>meso</i>-tetraphenylporphyrin P (both as free base and Zn<sup>II</sup> complex), carrying in 2 or 2,12 β-pyrrolic position an electron donor ferrocene (Fc), and/or an electron acceptor fullerene (C60) moiety, connected to the porphyrin core via an ethynyl or an ethynylphenyl spacer. We measured the NLO response by the electric-field-induced second-harmonic generation (EFISH) technique in CH<sub>2</sub>Cl<sub>2</sub> solution with a 1907 nm incident wavelength, recording for all the investigated compounds unexpected negative values of μβ<sub>1907</sub>. Since density functional theory (DFT) calculations evidenced for P-Fc dyads almost null ground state dipole moments and very low values for P-C60 dyads and Fc-P-C60 triads, our EFISH results suggested a significant contribution to γ<sub>EFISH</sub> of the purely electronic cubic term γ(−2ω; ω, ω, 0), which prevails on the quadratic dipolar orientational one μβ(−2ω; ω, ω)/5kT, as confirmed by computational evidence.https://www.mdpi.com/1996-1944/14/16/4404porphyrinsfullereneferrocenenonlinear opticshybrid materialsdyads |
| spellingShingle | Francesca Limosani Francesca Tessore Gabriele Di Carlo Alessandra Forni Pietro Tagliatesta Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials Materials porphyrins fullerene ferrocene nonlinear optics hybrid materials dyads |
| title | Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials |
| title_full | Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials |
| title_fullStr | Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials |
| title_full_unstemmed | Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials |
| title_short | Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials |
| title_sort | nonlinear optical properties of porphyrin fullerene and ferrocene hybrid materials |
| topic | porphyrins fullerene ferrocene nonlinear optics hybrid materials dyads |
| url | https://www.mdpi.com/1996-1944/14/16/4404 |
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