Regiochemically Controlled Synthesis of a β-4-β′ [70]Fullerene Bis-Adduct

Cerón, Maira R.; Castro, Edison; Neti, Venkata S. Pavan K.; Dunk, Paul W.; Echegoyen, Luís

doi:10.1021/acs.joc.6b02301

Cited by 8 publications

(3 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…First, we focused on the DA reaction in the absence of an electric field. Previous works have shown that the [6-6] rather than [5-6] bonds on C 60 are more feasible for cycloaddition. , Accordingly, here the monoaddition of indene takes place on a [6-6] bond, and the calculated barrier is 4.6 kcal mol –1 . For the formed IC 60 MA, as depicted in Figure , a total of eight different [6-6] sites can be detected and labeled as cis -1– cis -3, e , and trans -1– trans -4.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Studies of Regiocontrolled Bisaddition of Fullerenes Driven by Oriented External Electric Fields

Wang,

Zhao,

Ehara

2023

J. Org. Chem.

View full text Add to dashboard Cite

The challenge of achieving regioselective multifunctionalization on highly symmetric C 60 and C 70 fullerenes persists as a significant hurdle. In this study, we present a novel approach involving the participation of an oriented external electric field (OEEF) to facilitate the regioselective formation of bisadducts in C 60 /C 70 fullerenes. These products are obtained through consecutive Diels−Alder cycloaddition reactions. We constructed the field strength−barrier relationship and elucidated the OEEFdriven modulation mechanisms quantitatively. Leveraging the interplay between molecular dipoles and electric fields, the diverse reactions at distinct sites exhibit varying degrees of sensitivity to the applied electric fields, thereby leading to a pronounced regioselectivity in the bisaddition process. Our proposition suggests that the angle formed between the bonding direction (referred to as the reaction axis) and the external field can conveniently function as a predictive descriptor for the reactivity of different sites on the fullerene surface when subjected to electric fields.

show abstract

Section: Resultsmentioning

confidence: 99%

Mechanistic Studies of Regiocontrolled Bisaddition of Fullerenes Driven by Oriented External Electric Fields

Wang,

Zhao,

Ehara

2023

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…Recently, use of Diels–Alder reactions for introduction of anthracene units on fullerenes allows the regiochemically controlled synthesis of derivatives (regioisomers bis adducts); however, mass spectrometric analysis of these new compounds is still a challenge due to their extremely high lability . An alternative charge-acquisition channel in ET involves formation of radical anions, where migration of an electron from a primary matrix radical anion to the neutral analyte produces a negatively charged secondary ion.…”

Section: Results and Discussionmentioning

confidence: 99%

Electron-Transfer Ionization of Nanoparticles, Polymers, Porphyrins, and Fullerenes Using Synthetically Tunable α-Cyanophenylenevinylenes as UV MALDI-MS Matrices

Ramírez-Pradilla

Blanco‐Tirado

2019

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Electron-transfer ionization in matrix-assisted laser desorption/ionization (ET-MALDI) is widely used for the analysis of functional materials that are labile, unstable, and reactive in nature. However, conventional ET matrices (e.g., trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile (DCTB)) still lack in performance due to cluster formation, reactivity with analytes, and vacuum instability. In this contribution, we report the use of α-cyanophenylenevinylene derivatives as UV MALDI matrices for the analysis, by ET ionization, of nanoparticles, polymers, porphyrins, and fullerenes. The synthetic versatility of the phenylenevinylene (PV) core allowed us to modulate physicochemical properties, fundamental for efficient formation of primary ions in the gas phase under MALDI conditions, such as planarity, ionization potentials, molar absorptivity, and laser thresholds. For instance, introduction of −CN groups in vinyl positions of the PV core induced structural disruption in planarity in the new α-CNPV derivatives, shifting their maximum molar absorptivity to UV wavelengths and increasing their ionization energy values above 8.0 eV. UV MALDI-relevant photophysical properties in solution and solid state are reported (λmax and ε355nm). LDI spectra of α-CNPVs exhibit predominant signals due to M+• and [M + H]+ species, whereas the standard matrix DCTB shows peaks associated with clusters and nondesirable products. The mass spectrometry (MS) performance of six α-CNPV derivatives was assessed for the ionization of a standard compound, with α-CNPV-CH3 and α-CNPV-OCH3 exhibiting better analytical figures of merit than those of a standard matrix (DCTB). These new matrices display high vacuum stability (79%) for up to 240 min of residence in the ionization source, in contrast with DCTB with 13%. Vacuum stability is vital, particularly for applications such as high-throughput analysis and imaging MS. In addition, when a mixture of 20 analytes (PAHs, porphyrins, and triphenylamine dyes) ranging from m/z 300 to 1700 was analyzed via ET-MALDI, we observed analyte coverage of 90% with the α-CNPV-CH3 derivative, whereas DCTB afforded only 70%. Finally, α-CNPV-CH3 was tested and compared with DCTB, as ET-MALDI matrix for petroporphyrins, conjugated polymers, gold nanoparticles, and fullerene derivatives analysis, outperforming in most cases the standard matrix.

show abstract

“…More MX@Cn molecules have been identified in gas-phase MS spectra . Concerning the attachment of the fullerene to the electrodes, it is known that elliptical fullerenes in general are more prone to employ the carbon atoms on their curved poles in reactions because in this region carbon–carbon double bonds are strained due to the curvature of the molecules . To fabricate a device for frequent use one can attach C 70 or other ellipsoid fullerenes, encapsulated with an MX-type guest, to graphene ribbons to be used as primary electrodes.…”

Section: Conclusion and Prospectsmentioning

confidence: 99%

Fullerene-Based Switching Molecular Diodes Controlled by Oriented External Electric Fields

et al. 2019

View full text Add to dashboard Cite

Employing multiscale in silico modeling, we propose switching molecular diodes on the basis of endohedral fullerenes (fullerene switching diode, FSD), encapsulated with polar molecules of general type MX (M: metal, X: nonmetal) to be used for data storage and processing. Here, we demonstrate for MX@C70 systems that the relative orientation of enclosed MX with respect to a set of electrodes connected to the system can be controlled by application of oriented external electric field(s). We suggest systems with two- and four-terminal electrodes, in which the source and drain electrodes help the current to pass through the device and help the switching between the conductive states of FSD via applied voltage. The gate electrodes then assist the switching by effectively lowering the energy barrier between local minima via stabilizing the transition state of switching process if the applied voltage between the source and drain is insufficient to switch the MX inside the fullerene. Using nonequilibrium Green’s function combined with density functional theory (DFT-NEGF) computations, we further show that conductivity of the studied MX@C70 systems depends on the relative orientation of MX inside the cage with respect to the electrodes. Therefore, the orientation of the MX inside C70 can be both enforced (“written”) and retrieved (“read”) by applied voltage. The studied systems thus behave like voltage-sensitive switching molecular diodes, which is reminiscent of a molecular memristor.

show abstract

Regiochemically Controlled Synthesis of a β-4-β′ [70]Fullerene Bis-Adduct

Cited by 8 publications

References 34 publications

Mechanistic Studies of Regiocontrolled Bisaddition of Fullerenes Driven by Oriented External Electric Fields

Mechanistic Studies of Regiocontrolled Bisaddition of Fullerenes Driven by Oriented External Electric Fields

Electron-Transfer Ionization of Nanoparticles, Polymers, Porphyrins, and Fullerenes Using Synthetically Tunable α-Cyanophenylenevinylenes as UV MALDI-MS Matrices

Fullerene-Based Switching Molecular Diodes Controlled by Oriented External Electric Fields

Contact Info

Product

Resources

About