A Soluble Benzodifluoranthene Derivative by Dehydration of an Oxygen‐Bridged Precursor

The synthesis and structural characterization of the double-stranded carbon skeleton in the belt region of a C84 fullerene has been achieved. The synthetic methodology used is based on cyclic dimerization of diastereomeric AB-type monomers 18 by a non-diastereospecific Diels-Alder reaction with isobenzofuran and acenaphthylene groups as reactive termini. Four diasteromeric monomer precursors 17 were prepared for the first time by the use of dihydropyracylene (12) in a multistep synthesis. The synthesis of dihydropyracylene itself has been optimized to the degree that it is now available on the 10 g scale. The belt-shaped macrocycle 19, obtained from dimerization of the monomers 17, could be partly aromatized by an acid-catalyzed dehydration reaction to give 23, which differs from the fully unsaturated belt by two water molecules. Semiempirical AM1 calculations of the electronic and thermodynamic properties of cyclic fluoranthenes revealed strain energy as the essential reason for the incomplete aromatization of 19. The structures of the macrocycles 19 and 23, one of the monomer precursors, and two diastereomeric epoxybenzo[k]fluoranthenes were elucidated by single-crystal X-ray crystallography.

Section: Resultsmentioning

confidence: 99%

The Carbon Skeleton of the Belt Region of Fullerene C₈₄ (D₂)

Neudorff

Lentz

Anibarro

et al. 2003

“…[8] Table 2 presents the calculated hole electronic couplings (t + s) and hole mobilities (m + s) based on dimers that are extracted from single crystalline structures. The molecular packings of TES-ADT and DF-TES-ADT are typical 2-D p-stackings with two types of dimer in crystalline structures (Figure 3).…”

Section: B)mentioning

confidence: 99%

“…The electronic coupling (t) and charge mobility (m) of soluble 8,17-di-n-hexylbenzo[1,2-k;4,5-k']difluoranthene (DH-BDF) is also estimated based on the single crystal structure. [8] A Comparison with silylethynylated ADTs indicates that DH-BDF may be a soluble, stable and high-performance p-channel organic semiconductor. Figure 1 summarizes the chemical structures of the compounds studied herein, and presents their abbreviations.…”

mentioning

confidence: 99%

High‐Performance p‐Channel Organic Semiconducting Candidates Based on Benzo[1,2‐k;4,5‐k′]difluoranthene Derivatives

Liu

Kuo

2009

Orbital promises: Frontier orbital analyses showed that the small lambda(+) value of 8,17-di-n-hexylbenzo[1,2-k;4,5-k']difluoranthene (DH-BDF) is owed to the nonbonding character of the BDF framework. The calculated adiabatic ionic potential and hole mobility indicates that this compound is a p-type air-stable organic field-effect transistor, which promises to be a soluble, stable and high-performance p-type organic semiconductor.

“…[32] Syntheses of 7,9,16,18-tetraphenylbenzo[1,2-k:4,5-k']difluoranthene (24 ae), [30] 7,9,16,18-tetrakisA (25), [34] and 6,8,15,17-tetraphenyl-1.18,4.5,9.10,13.14-tetrabenzoheptacene (26) [35] have been reported elsewhere. Compounds 24 ie and 25 were prepared by a lengthy synthetic process and the method for the generation of 7,9,16,18-tetraphenylbenzo[1,2-k:4,5-k']difluoranthene (24 ae) has not been clearly elucidated.…”

Section: Resultsmentioning

confidence: 99%

“…The torsion angle of the central anthracene core, measured at C7-C7 A-C13 A-C13, and the dihedral angle associated with the two naphthalene planes in 24 je are 12.48 and 21.18, respectively, whereas 8,17-di-n-hexylbenzo[1,2-k:4,5-k']difluoranthene (25) has an almost planar structure. [34] p-p stacking is an usual intermolecular interaction in PAHs. [42] In the five compounds listed in Table 4, the skeletons and substituents display different forms of packing and only 17 ab exhibits significant p-p interaction.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structures, and Physical Properties of Benzo[k]fluoranthene‐Based Linear Acenes

Kung

Cheng

Tai

et al. 2010

This work describes the syntheses, crystal structures, photophysical properties, and electro-chemical analyses of benzo[k]fluoranthene-based linear acenes, together with ab initio density functional theory computations on them. The molecules were prepared in generally moderate to good yields through Pd-catalyzed cycloadditions between 1,8-diethynylnaphthalene derivatives and aryl iodides. This protocol is simpler and more efficient than conventional methods. The scope and limitations of this reaction were examined. The structures of compounds 4hb, 15ac, 17ab, 19ac, and 24je were determined by X-ray analysis; they are either bent or twisted, rather than planar. The photophysical and electrochemical properties of these cycloadducts were also investigated and compared with computational predictions based on density functional theory.