Selective Electrochemical Retro‐Cycloaddition Reaction of Pyrrolidinofullerenes

Lukoyanova, Olena; Cardona, Claudia M.; Altable, Margarita; Filippone, Salvatore; Domenech, Ángel Martín; Martı́n, Nazario; Echegoyen, Luís

doi:10.1002/anie.200602431

Cited by 63 publications

(34 citation statements)

References 24 publications

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“…Possibly, the excess C 60 needed for formation of 4 promotes a retro-Prato reaction as the reaction time is extended, as previously reported. 74 The optimal reaction time was found to be 6 h, after which Cu-free rotaxane 4 was isolated in 13% yield after several chromatographic purification steps.…”

Section: Resultsmentioning

confidence: 98%

Topological and Conformational Effects on Electron Transfer Dynamics in Porphyrin-[60]Fullerene Interlocked Systems

et al. 2012

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The effect of molecular topology, and conformation on the dynamics of photoinduced electron transfer (ET) processes has been studied in interlocked electron donor-acceptor systems, specifically rotaxanes with zinc(II)-tetraphenylporphyrin (ZnP) electron donor and [60]fullerene (C60) as the electron acceptor. Formation or cleavage of coordinative bonds was used to induce major topological and conformational changes in the interlocked architecture. In the first approach, the tweezers-like structure created by the two ZnP stopper groups on the thread was used as a recognition site for complexation of 1,4-diazabicyclo[2.2.2]octane (DABCO), which creates a bridge between the two ZnP moieties on the rotaxane, generating a catenane structure. The photoinduced processes in the DABCO-complexed (ZnP)2-[2]catenate-C60 system were compared with those of the (ZnP)2-rotaxane-C60 precursor and the previously reported ZnP-[2]catenate-C60. Steady-state emission and transient absorption studies showed that a similar multistep ET pathway emerged for rotaxanes and catenanes upon photoexcitation at various wavelengths, ultimately resulting in a long-lived ZnP•+/C60•− charge separated radical pair state. However, the decay kinetics of the latter states clearly reflect the topological differences between the rotaxane, the catenate, and DABCO-complexed-catenate architectures. The lifetime of the long-distance ZnP•+–[Cu(I)phen2]+–C60•− charge separated state is more than four times longer in 3 (1.03 µs) than in 1 (0.24 µs) and approaches that in catenate 2 (1.1 µs). The results clearly showed that adoption of a catenane from a rotaxane topology inhibits the charge recombination process. In a second approach, the Cu(I) ion used as template to assemble the (ZnP)2–[Cu(I)phen2]+–C60 rotaxane was removed, and structural analysis suggested a major topographical change occurred, such that charge separation between the chromophores was no longer observed upon photoexcitation in nonpolar as well as polar solvents. Only ZnP and C60 triplet excited states were observed upon laser excitation. These results highlighted the critical importance of the central Cu(I) ion for long range ET processes in these large interlocked electron donor-acceptor systems.

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Section: Resultsmentioning

confidence: 98%

Topological and Conformational Effects on Electron Transfer Dynamics in Porphyrin-[60]Fullerene Interlocked Systems

et al. 2012

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“…It is worth noting that the second irreversible oxidation process is observed at approximately +1.2 V, which is close to the first oxidation potential of PCBM (+1.24 V versus Fc +/0 ). It has been reported that controlled‐potential electrolysis of fulleropyrrolidines and methanofullerenes at their first oxidation potentials results in retro‐cycloaddition with methano bridge cleavage …”

Section: Resultsmentioning

confidence: 99%

“…It has been reported that controlled-potential electrolysis of fulleropyrrolidines and methanofullerenes at their first oxidation potentials results in retrocycloaddition with methano bridge cleavage. [44,45] Double-caged compounds 1a-d demonstrate two irreversible oxidationp eaks at the same positions as fulleroproline esters 2a-d (approximately 1.0 and1 .2 Vv ersusF c + /0 ). Similarly to fulleroproline esters, oxidationi sf ollowed by compound degradation.…”

Section: Electrochemical and Spectroscopic Behaviormentioning

confidence: 98%

“…The CV curves of fulleroprolinee sters 2a-d are similar to the vast majority of fullerenem onocycloadducts. [41][42][43] They show three electrochemically reversible one-electron reduction steps separated by 0.4-0.5 V. Relative to the parentC 60 ,t he first reductionp eak is shifted by À0.07 V. Oxidation of fulleroproline esters is observed as an irreversible process at approximately 1.0 Vv ersus Fc + /0 and corresponds to abstraction of an electron from the nitrogen lone-electron pair, [43,44] the first oxidation potential value being negatively shiftedb ya pproximately 0.2 Vw ith respect to that of PCBM.I ti sw orth noting that the second irreversible oxidation process is observed at approxi-mately + 1.2 V, which is close to the first oxidationp otentialo f PCBM (+ 1.24 Vv ersusF c + /0 ). It has been reported that controlled-potential electrolysis of fulleropyrrolidines and methanofullerenes at their first oxidation potentials results in retrocycloaddition with methano bridge cleavage.…”

Section: Electrochemical and Spectroscopic Behaviormentioning

confidence: 99%

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Tightly Bound Double‐Caged [60]Fullerene Derivatives with Enhanced Solubility: Structural Features and Application in Solar Cells

Brotsman

Ioutsi

Rybalchenko

et al. 2017

Chemistry An Asian Journal

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A series of novel highly soluble double-caged [60]fullerene derivatives were prepared by means of lithium-salt-assisted [2+3] cycloaddition. The bispheric molecules feature rigid linking of the fullerene spheres through a four-membered cycle and a pyrrolizidine bridge with an ester function CO R (R=n-decyl, n-octadecyl, benzyl, and n-butyl; compounds 1 a-d, respectively), as demonstrated by NMR spectroscopy and X-ray diffraction. Cyclic voltammetry studies revealed three closely overlapping pairs of reversible peaks owing to consecutive one-electron reductions of fullerene cages, as well as an irreversible oxidation peak attributed to abstraction of an electron from the nitrogen lone-electron pair. Owing to charge delocalization over both carbon cages, compounds 1 a-d are characterized by upshifted energies of frontier molecular orbitals, a narrowed bandgap, and reduced electron-transfer reorganization energy relative to pristine C . Neat thin films of the n-decyl compound 1 a demonstrated electron mobility of (1.3±0.4)×10 cm V s , which was comparable to phenyl-C -butyric acid methyl ester (PCBM) and thus potentially advantageous for organic solar cells (OSC). Application of 1 in OSC allowed a twofold increase in the power conversion efficiencies of as-cast poly(3-hexylthiophene-2,5-diyl) (P3HT)/1 devices relative to the as-cast P3HT/PCBM ones. This is attributed to the good solubility of 1 and their enhanced charge-transport properties - both intramolecular, owing to tightly linked fullerene cages, and intermolecular, owing to the large number of close contacts between the neighboring double-caged molecules. Test P3HT/1 OSCs demonstrated power-conversion efficiencies up to 2.6 % (1 a). Surprisingly low optimal content of double-caged fullerene acceptor 1 in the photoactive layer (≈30 wt %) favored better light harvesting and carrier transport owing to the greater content of P3HT and its higher degree of crystallinity.

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“…The retro‐cycloaddition process can be also promoted under electrochemical conditions. Thus, controlled potential electrolysis (CPE) for the removal of pyrrolidine moieties from pyrrolidinofullerene derivatives has been reported …”

Section: Methodsmentioning

confidence: 99%

Competitive retro‐cycloaddition reactions in heterocyclic fullerene bis‐adducts ions: selective removal of the heterocyclic moieties

Suárez

Maroto

Filippone

et al. 2015

Rapid Comm Mass Spectrometry

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Selective Electrochemical Retro‐Cycloaddition Reaction of Pyrrolidinofullerenes

Cited by 63 publications

References 24 publications

Topological and Conformational Effects on Electron Transfer Dynamics in Porphyrin-[60]Fullerene Interlocked Systems

Topological and Conformational Effects on Electron Transfer Dynamics in Porphyrin-[60]Fullerene Interlocked Systems

Tightly Bound Double‐Caged [60]Fullerene Derivatives with Enhanced Solubility: Structural Features and Application in Solar Cells

Competitive retro‐cycloaddition reactions in heterocyclic fullerene bis‐adducts ions: selective removal of the heterocyclic moieties

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