Synthesis and properties of covalently linked thiaporphyrin–ferrocene conjugates

Lakshmi, Vellanki; Santosh, G.; Ravikanth, Mangalampalli

doi:10.1016/j.jorganchem.2010.10.028

Cited by 16 publications

(8 citation statements)

References 24 publications

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“…32 Previous studies have demonstrated off/on switching of fluorescence in the directly bound meso-substituted Fc-ZnP system via electrochemical or chemical redox control upon addition of Ce(IV), as illustrated in Scheme 2. 50 Off/on fluorescence switching is observed for all mesoferrocenyl-porphyrin conjugates here studied. In contrast to the quantitative quenching observed for all meso-ferrocenyl porphyrins, the extent of fluorescence recovery for their ferricenium counterparts displays a strong dependence on the nature of the π-linker involved.…”

Section: ■ Experimental Sectionmentioning

confidence: 80%

“…The broadness of this signal is most likely due to the presence of multiple ruffled macrocycle configurations. 50 The analogous β-pyrrole protons in closest proximity to the vinyl-ferrocenyl and ethynyl-ferrocenyl substitutents display sharper resolved doublet signals shifted upfield of the latter at 9.65 and 9.84 ppm, respectively, indicative of lesser ruffling in the macrocycle. In contrast, all β-pyrrole protons are observed in a narrow range from 8.89−9.05 ppm for the Fc-Ph-ZnP system.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Synthesis, Electronic and Photophysical Characterization of π-Conjugated meso-Ferrocenyl-porphyrin Fluorescent Redox Switches

et al. 2014

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A series of meso-ferrocenyl-porphyrin dyads linked by four different π-conjugated bridging units (directly bound, vinyl, ethynyl, and phenyl) have been synthesized to investigate the influence of the conjugated linker on both the electronic and photochemical properties of the porphyrin chromophore. The basic structure consists of 5-(Fc)-15-(4-methylbenzoate)-10,20-diphenylporphyrin zinc(II), where Fc = ferrocene, vinylferrocene, ethynylferrocene, or phenylferrocene. Upon introduction of the various electron-donating ferrocenyl moieties at the meso-position of the porphyrin ring, Soret and Q-band electronic transitions of the resultant dyads are red-shifted compared with those of the nonferrocenyl reference porphyrin system 15-(4-methylbenzoate)-10,20-diphenylporphyrin zinc(II). The electronic properties of these systems have been investigated by electrochemical (cyclic voltammetry) and computational (DFT/TDDFT) methods, while UV/vis absorption and fluorescence emission spectroscopic analysis is also presented. Collectively, electronic and photophysical analysis indicate a strong electronic communication between the porphyrin macrocycle and directly bound ferrocenyl, vinylferrocenyl, and ethynylferrocenyl dyads. The presence of a phenyl spacer acts to inhibit such electronic communication due to the orthogonal geometry of the bridging phenyl ring at the meso-position of the porphyrin macrocycle. In addition to electronic factors, and in particular for the directly bound 5-(ferrocenyl)-15-(4-methylbenzoate)-10,20-diphenylporphyrin zinc(II) dyad, computational analysis suggests that a significant ruffling of the porphyrin macrocyle from planarity is required to facilitate the bulky ferrocene group directly at the meso-position. Of particular note for each of the meso-ferrocenyl-porphyrin dyads is how fluorescence emission derived from the porphyrin S1 (π–π*) excited state is quantitatively quenched due to photoinduced charge-transfer from the ferrocene unit onto the excited state porphyrin. Spectroelectrochemical studies demonstrate redox off/on switching of the porphyrin fluorescence emission via ferricenium/ferrocene redox cycling. Interestingly, it was found that the S0 ← S1 fluorescence emission is also switched-on following titration with the metal ions Ce(IV), Cu(II), and Fe(III) in acetonitrile.

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Section: ■ Experimental Sectionmentioning

confidence: 80%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis, Electronic and Photophysical Characterization of π-Conjugated meso-Ferrocenyl-porphyrin Fluorescent Redox Switches

et al. 2014

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“…62,63 Luminescence control of porphyrin units was previously reported in different dyads involving a tetrathiafulvalene (TTF) 19,64,65 and ferrocene redox units. 66,67 More recently studies with redox active iron or ruthenium acetylides metal complexes were reported. 68,69 In all cases, the fluorescence of the porphyrin is partially or totally quenched in the neutral state of the nearby redox unit and is restored upon oxidation of the latter.…”

Section: Chart 1 Structures Of the Two Systems Investigated In This mentioning

confidence: 99%

Redox-driven porphyrin based systems for new luminescent molecular switches

et al. 2018

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In this work, we explore the possibility of tuning the fluorescence intensity of two porphyrin systems through the electrochemical oxidation of an appended ruthenium acetylide bridge. Two electrochemically switchable systems, a dyad (ZnP-Ru, 3) and a triad (ZnP-Ru-P2H, 5), were prepared and investigated. In the ZnP-Ru dyad, the fluorescence of the zinc porphyrin was switched reversibly between the ON and OFF state upon the oxidation of the ruthenium unit, the most probable quenching process involved after oxidation being the electron transfer from the singlet excited state of ZnP to the oxidized ruthenium center. In the ZnP-Ru-P2H triad, we show that both porphyrins' fluorescence are highly quenched independent of the redox state of the ruthenium bridge owing to the efficient photoinduced charge transfer within the ruthenium complex.

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“…The pyridin‐2(1 H )‐one derivatives have been found to exhibit interesting biological activities such as kappa opioid receptor agonists , antitumor agents , farnesyltransferase inhibitors , and cardiotonic agents . It is now well established that the incorporation of ferrocene units in organic molecules introduces significant and new properties in these materials . The introduction of ferrocenyl group on the 2(1 H )‐pyridone ring may lead to novel biological activities.…”

Section: Introductionmentioning

confidence: 99%

Microwave‐Assisted Aqueous Synthesis of 6‐Ferrocenyl Pyridin‐2(1H)‐one Derivative

Zhang

Ding

et al. 2013

Journal of Heterocyclic Chem

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Synthesis and properties of covalently linked thiaporphyrin–ferrocene conjugates

Cited by 16 publications

References 24 publications

Synthesis, Electronic and Photophysical Characterization of π-Conjugated meso-Ferrocenyl-porphyrin Fluorescent Redox Switches

Synthesis, Electronic and Photophysical Characterization of π-Conjugated meso-Ferrocenyl-porphyrin Fluorescent Redox Switches

Redox-driven porphyrin based systems for new luminescent molecular switches

Microwave‐Assisted Aqueous Synthesis of 6‐Ferrocenyl Pyridin‐2(1H)‐one Derivative

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