Synthesis and Characterization of the Three Dicyclopentapyrenes<sup>1</sup>

and, Lawrence T. Scott; Necula, Atena

doi:10.1021/jo9516087

Cited by 102 publications

(40 citation statements)

References 15 publications

(27 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The computed AEAs show that CP-PAHs represent an interesting class of electron acceptors. Since CPPAHs are readily accessible [1,2,9,10,18] and their AEAs can be enhanced further by substitution of the perimeter hydrogens [32,33], (functionalized) CP-PAHs are timely synthetic targets for novel n-type materials, viz. strong oxidants.…”

Section: Discussionmentioning

confidence: 99%

“…This is of interest since CP-PAHs have been identified as prevalent environmental pollutants that are invariably generated during incomplete combustion processes [8]. Recently, the dicyclopentapyrenes 7 and 8 [9,10] (Fig. 1) were unexpectedly found to exert direct-acting mutagenicity in bacterial assays [11].…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, we were prompted to compute AEAs of a representative series of (CP)-PAHs at the ab initio B3LYP/DZP++ level of theory [14][15][16][17]. We here report and discuss the gas phase AEAs with and without zero-point vibrational energy (ZPVE) [9,10] and the bowl-shaped corannulene (9) [19,20] (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

Todorov

Koper

Lenthe

et al. 2008

Chemical Physics Letters

View full text Add to dashboard Cite

The B3LYP/DZP++ adiabatic electron affinity (AEA) of nine (non)-alternant polycyclic aromatic hydrocarbons are reported and discussed. Calculations became feasible for molecules this size by projecting out the near-linearly dependent part of the one-electron basis. Non-alternant PAH consisting of an alternant PAH core modified by peri-annulation with unsaturated five-membered rings (CP-PAHs) possess markedly enhanced AEAs.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

Todorov

Koper

Lenthe

et al. 2008

Chemical Physics Letters

View full text Add to dashboard Cite

show abstract

“…The electron affinity, A, corresponds to the energy of the LUMO in eV, F is the Faraday and C is a constant that includes terms similar to those described in equation (1). An attempt was made to correlate the reduction potentials with the simple Hückel LUMO energies of a limited number of sterically constrained, even alternant PAH.…”

Section: Methodsmentioning

confidence: 99%

“…These compounds have received renewed interest because the techniques of flash vacuum thermolysis have allowed the synthesis of new compounds whose chemistry is unexplored. 1 A broader understanding of the chemistry of buckminsterfullerene, a CPAH, may also be reflected in studies of simpler CPAH. The reactivity of even, non-alternant CPAH is frequently different from that of even alternant PAH.…”

Section: Introductionmentioning

confidence: 99%

Electron transfer properties of non-alternant, substituted compounds related to fluoranthene. Experimental determination and theoretical modeling of electrochemical oxidation and reduction potentials in non-aqueous solution

Steffen

Plummer

Braley

et al. 1997

J. Phys. Org. Chem.

View full text Add to dashboard Cite

The oxidation and reduction potentials of a series of related even non-alternant derivatives of 7,14-disubstituted acenaphth[1,2-k] fluoranthenes, and also fluoranthene, 7,10-diphenylfluoranthene and 8,9-dihydrodiindeno[1,2-j;2Ј,1Ј-] fluoranthene, were determined in organic solvents by cyclic voltammetry. The effects of steric hindrance on conjugation of the substituents with the central polycyclic aromatic hydrocarbon nucleus were evaluated. The semi-empirical molecular orbital calculation programs OMEGAMO, Extended Hückel, AM1 and PM3 were used to obtain optimal geometries and calculated HOMO and LUMO energies. As a further refinement, COSMO solvation was included in the AM1 calculations. The redox properties were correlated with data derived from the various semi-empirical calculations and the quality of these correlations is discussed. Inclusion of solvation energies in the computed molecular orbital energies results in a significant improvement in the correlation between observed and calculated oxidation potentials.

show abstract

Flash Vacuum Thermolysis of Acenaphtho[1,2-a]acenaphthylene, Fluoranthene, Benzo[k]- and Benzo[j]fluoranthene – Homolytic Scission of Carbon-Carbon Single Bonds of Internally Fused Cyclopenta Moieties atT ≥ 1100 °C

et al. 1999

View full text Add to dashboard Cite

Flash vacuum thermolysis (FVT, 1000 °C ≥ T ≥ 1200 °C) of acenaphtho[1,2‐a]acenaphthylene (3, C22H12) gave the C22H12 cyclopenta‐fused polycyclic aromatic hydrocarbon (CP‐PAH) acenaphtho[1,2‐e]acenaphthylene (4), cyclopenta[cd]perylene (5) and cyclopenta[def]benzo[hi]chrysene (6). Whereas the formation of 4 is explained by a ring contraction/ring expansion rearrangement of 3, the identification of 5 and 6 suggests that 3 also undergoes homolytic scission of a five‐membered ring's Carbon‐Carbon single bond furnishing the transient diradical intermediate 7. Ring closure of 7to form 8 after rotation around the Carbon‐Carbon single bond of the intact five‐membered ring followed by hydrogen shifts will give 6. The latter can rearrange subsequently into 5by ring contraction/ring expansion. The structural assignment of 4 and 5 was supported by independent FVT of 6,12‐bis(1‐chloroethenyl)chrysene (14) and 3‐(1‐chloroethenyl)perylene (23), respectively. FVT of 14 (900–1200 °C) gave in a consecutive process 6,12‐bis(ethynyl)chrysene (15), 9‐ethynylbenz[j]acephenanthrylene (16) and bis(cyclopenta[hi,qr])chrysene (17). Although at T ≥ 900 °C 17 selectively rearranges into 4 by ring contraction/ring expansion, at 1200 °C the latter is converted into 5 presumably via a diradical intermediate obtained by homolytic scission of a single Carbon‐Carbon bond of a five‐membered ring. FVT of 23 gave in situ 3‐ethynylperylene (25), which at 1000 °C is nearly quantitatively converted into 5. The propensity of internal cyclopenta moieties to undergo homolytic scission of a five‐membered ring′s Carbon‐Carbon single bond was corroborated by independent FVT of benzo[k]‐ (11) and benzo[j]fluoranthene (12). Previously unknown thermal pathways to important (CP)‐PAH combustion effluents are disclosed at T ≥ 1000 °C.

show abstract

Synthesis and Characterization of the Three Dicyclopentapyrenes¹

Cited by 102 publications

References 15 publications

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

Electron transfer properties of non-alternant, substituted compounds related to fluoranthene. Experimental determination and theoretical modeling of electrochemical oxidation and reduction potentials in non-aqueous solution

Flash Vacuum Thermolysis of Acenaphtho[1,2-a]acenaphthylene, Fluoranthene, Benzo[k]- and Benzo[j]fluoranthene – Homolytic Scission of Carbon-Carbon Single Bonds of Internally Fused Cyclopenta Moieties atT ≥ 1100 °C

Contact Info

Product

Resources

About

Synthesis and Characterization of the Three Dicyclopentapyrenes1

Cited by 102 publications

References 15 publications

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

Electron transfer properties of non-alternant, substituted compounds related to fluoranthene. Experimental determination and theoretical modeling of electrochemical oxidation and reduction potentials in non-aqueous solution

Flash Vacuum Thermolysis of Acenaphtho[1,2-a]acenaphthylene, Fluoranthene, Benzo[k]- and Benzo[j]fluoranthene – Homolytic Scission of Carbon-Carbon Single Bonds of Internally Fused Cyclopenta Moieties atT ≥ 1100 °C

Contact Info

Product

Resources

About

Synthesis and Characterization of the Three Dicyclopentapyrenes¹