Synthesis and characterization of new ferrocene, porphyrin and C60 triads, connected by triple bonds

Tagliatesta, Pietro; Pizzoferrato, R.

doi:10.1016/j.jorganchem.2015.04.006

Cited by 10 publications

(14 citation statements)

References 28 publications

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“…Recently the beta functionalization of H 2 TPP by one or two ferrocene molecules in the 2 and 3 positions through ethynyl or phenylethynyl groups was reported by some of us . Two new triads, connecting ferrocene and C60 to the 2,12 pyrrole positions of H 2 TPP through ethynyl bonds were obtained and used as models to further investigate their electron‐transfer properties . Reports from other groups have followed on the synthesis and characterization of different tetraphenylporphyrins bearing ferrocene at beta, meso or 4‐phenyl positions ,,.…”

Section: Resultsmentioning

confidence: 99%

“…[16] Two new triads, connecting ferrocene and C60 to the 2,12 pyrrole positions of H 2 TPP through ethynyl bonds were obtained and used as models to further investigate their electron-transfer properties. [17] Reports from other groups have followed on the synthesis and characterization of different tetraphenylporphyrins bearing ferrocene at beta, meso or 4-phenyl positions. [11,18,19] The correct stereochemistry of 2,12-dibromo TPP starting compound was recently elucidated.…”

Section: Resultsmentioning

confidence: 99%

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Functionalization of Carbon Spheres with a Porphyrin−Ferrocene Dyad

et al. 2018

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Meso-tetraphenylporphyrin connected with a ferrocene molecule in the beta-position of the macrocycle through a triple carbon-carbon bond has been bound to carbon spheres using the Prato-Maggini reaction. The ethynyl or/and phenylene ethynylene subunits were chosen as a linking bridge to give a high conjugation degree between the donor (i. e., ferrocene), the photoactive compound (i. e., porphyrin), and the acceptor (i. e., carbon spheres). The molecular bridges have been directly linked to the beta-pyrrole positions of the porphyrin ring, generating a new example of a long-range donor-acceptor system. Steady-state fluorescence studies together with Raman and XPS measurements helped understanding the chemical and physical properties of the porphyrin ring in the new adduct. The spectroscopic characteristics were also compared with those obtained from a similar compound bearing fullerene instead of carbon spheres.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Functionalization of Carbon Spheres with a Porphyrin−Ferrocene Dyad

et al. 2018

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“…Dyads 6-C60 and 6(Zn)-C60 were synthetized and characterized as reported in [ 36 ]. Triads 10a-C60, 10a(Zn)-C60, 10b-C60, 10b(Zn)-C60 were synthetized and characterized as reported in [ 46 ]. Their NMR, MS and UV spectra were in accordance with those previously reported (see Supplementary Materials, Figures S1–S6 and S9–S16 , and the elemental analyses).…”

Section: Methodsmentioning

confidence: 99%

“…The incident wavelength at 1.907 µm was obtained by Raman shifting the 1.064 µm emission of a Q-switched Nd:YAG laser in a high-pressure hydrogen cell (60 bar). The 1.907 μm laser incident wavelength was chosen because its second harmonic (at 953 nm) was far enough from the absorption bands of the chromophores in CH 2 Cl 2 [ 46 ] to avoid any enhancement of the second-order NLO response because of resonance. The Maker fringe pattern (that is the harmonic intensity variation as a function of the cell translation) was obtained through a liquid cell with thick windows in the wedge configuration.…”

Section: Methodsmentioning

confidence: 99%

“…In Fc-P-C60 triads a high charge delocalization of the π-electrons between the donor Fc and the acceptor C60 moieties is reached by linking them to the 2,12 β-pyrrolic positions of P through an ethynyl or an ethynylphenyl spacer [ 46 ], thus constituting an efficient approach to the modulation of electron donor–acceptor interactions to realize hybrid materials [ 47 , 48 , 49 , 50 , 51 , 52 ].…”

Section: Introductionmentioning

confidence: 99%

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Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials

et al. 2021

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In this research, we investigated the second-order nonlinear optical (NLO) properties of multicomponent hybrid materials formed by meso-tetraphenylporphyrin P (both as free base and ZnII 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 CH2Cl2 solution with a 1907 nm incident wavelength, recording for all the investigated compounds unexpected negative values of μβ1907. 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 γEFISH 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.

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Push–Pull Porphyrins via β‐Pyrrole Functionalization: Evidence of Excited State Events Leading to High‐Potential Charge‐Separated States

Sekaran

Jang

Misra

et al. 2019

Chemistry A European J

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A new set of free‐base and zinc(II)‐metallated, β‐pyrrole‐functionalized unsymmetrical push–pull porphyrins were designed and synthesized via β‐mono‐ and dibrominated tetraphenylporphyrins using Sonogashira cross‐coupling reactions. The ability of donors and acceptors on the push–pull porphyrins to produce high‐potential charge separated states was investigated. The porphyrins were functionalized at the opposite β,β′‐pyrrole positions of porphyrin ring bearing triphenylamine push groups and naphthalimide pull groups. Systematic studies involving optical absorption, steady‐state and time‐resolved emission revealed existence of intramolecular type interactions both in the ground and excited states. The push–pull nature of the molecular systems was supported by frontier orbitals generated on optimized structures, wherein delocalization of HOMO over the push group and LUMO over the pull group connecting the porphyrin π‐system was witnessed. Electrochemical studies were performed to visualize the effect of push and pull groups on the overall redox potentials of the porphyrins. Spectroelectrochemical studies combined with frontier orbitals helped in characterizing the one‐electron oxidized and reduced porphyrins. Finally, by performing transient absorption studies in polar benzonitrile, the ability of push–pull porphyrins to produce charge‐separated states upon photoexcitation was confirmed and the measured rates were in the range of 109 s−1. The lifetime of the final charge separated state was around 5 ns. This study ascertains the importance of push–pull porphyrins in solar energy conversion and diverse optoelectronic applications, for which high‐potential charge‐separated states are warranted.

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Synthesis and characterization of new ferrocene, porphyrin and C60 triads, connected by triple bonds

Cited by 10 publications

References 28 publications

Functionalization of Carbon Spheres with a Porphyrin−Ferrocene Dyad

Functionalization of Carbon Spheres with a Porphyrin−Ferrocene Dyad

Nonlinear Optical Properties of Porphyrin, Fullerene and Ferrocene Hybrid Materials

Push–Pull Porphyrins via β‐Pyrrole Functionalization: Evidence of Excited State Events Leading to High‐Potential Charge‐Separated States

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