Structure−Property Relationships in Phosphole-Containing π-Conjugated Systems:  A Quantum Chemical Study

Delaere, David; Nguyen, Minh Tho; Vanquickenborne, L. G.

doi:10.1021/jp026227t

Cited by 55 publications

(24 citation statements)

References 24 publications

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“…All atoms were augmented with a single set of polarisation functions. Several publications have shown that the hybrid functional B3LYP is adequate for studying the electronic structures of π-conjugated systems such as those involving a phosphole moiety, [34] EDOT [35] or π-conjugated oligomers. [36] Second derivatives were calculated in order to check that the optimised structures are true minima on the potential energy surface.…”

Section: Theoretical Sectionmentioning

confidence: 99%

How to Build Fully π‐Conjugated Architectures with Thienylene and Phenylene Fragments

et al. 2007

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A series of small-sized model π-conjugated oligomers have been prepared from thienylene and phenylene or dimethylor dimethoxy-substituted phenylene units. Crystallographic data for the methoxylated compound show a quasi-planar conformation with a non-covalent S-O interaction. The resulting strong conjugation in the gas phase has also been highlighted by UV/photoelectron spectroscopy and theoretical calculations (DFT). Indeed, for these compounds there is a large energy gap ∆E π arising from the interaction between the molecular orbitals of the isolated thienylene-phenylene species. This can be explained in terms of the energies of the two π orbitals of the dimethoxyphenylene unit, the shape of these molecular orbitals in a three-orbital interaction diagram and by the presence of the S···O interaction which re-

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Section: Theoretical Sectionmentioning

confidence: 99%

How to Build Fully π‐Conjugated Architectures with Thienylene and Phenylene Fragments

et al. 2007

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“…[6] Theoretical studies on the phosphole-containing p-conjugated systems have promoted a better understanding of their structure-property relationships. [7] In addition to the above 2,5-disubstituted systems, ringfused p-systems, such as dibenzoA C H T U N G T R E N N U N G [b,d]phospholes and dithienoA C H T U N G T R E N N U N G [b,d]phospholes, have been receiving growing interest, as they possess rigid and elongated p-networks that are prerequisite for exhibiting high light-emitting ability. [8,9] In particular, Baumgartners dithienoA C H T U N G T R E N N U N G [b,d]phospholes have proven to emit intense fluorescence covering the blueyellow region.…”

Section: Introductionmentioning

confidence: 99%

Comparative Study on the Structural, Optical, and Electrochemical Properties of Bithiophene‐Fused Benzo[c]phospholes

Matano

Miyajima

Fukushima

et al. 2008

Chemistry A European J

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Three types of bithiophene-fused benzo[c]phospholes were successfully prepared by Ti(II)-mediated cyclization of the corresponding dialkynylated bithiophene derivatives as a key step. Each sigma(3)-phosphorus center of the benzo[c]phosphole subunits was readily transformed into sigma(4)-phosphorus center by Au coordination or oxygenation. In addition, the bithiophene subunit was functionalized at the alpha,alpha'-carbon atoms by Pd-catalyzed cross-coupling reactions with heteroarylmetals and by an S(N)Ar reaction with hexafluorobenzene. The experimentally observed results (NMR spectroscopy, X-ray analysis, UV/Vis absorption/fluorescence spectroscopy, and cyclic/differential-pulse voltammetry) have revealed that the structural, optical, and electrochemical properties of the bithiophene-fused benzo[c]phospholes vary considerably depending on the pi-conjugation modes at the bithiophene subunits and the substituents of the heterocyclopentadiene components. The appropriately ring-annulated sigma(3)-P derivatives and sigma(4)-P-AuCl complexes were found to emit fluorescence in the orange-red region, and the sigma(4)-P-oxo derivatives proved to undergo reversible one-electron reduction at -1.4 to -1.8 V (vs ferrocene/ferrocenium). These results indicate that the bithiophene-fused benzo[c]phospholes possess narrow HOMO-LUMO gaps and low-lying LUMOs, which was confirmed by density functional theory calculations of their model compounds. The time-of-flight measurement of an ITO/benzo[c]phosphole/Al device showed that the electron mobility in the P-oxo derivative is one-order higher than that in Alq(3) at low electric fields. The present study demonstrates that the arene-fused benzo[c]phosphole skeleton could be a highly promising platform for the construction of a new class of phosphole-based optoelectrochemical materials.

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“…The energy of these absorptions, attributed to p-p* transitions [8], depends dramatically on the nature of the 2,5-substituants of the phosphole ring (Table 1) [6,7]. The values of k max and the optical end absorption k onset (the solution optical 'HOMO-LUMO' gap) [1e], become red-shifted on replacing the 2-pyridyl groups (k max = 390 nm) by 2-thienyl rings (k max = 412 nm).…”

Section: Physical Propertiesmentioning

confidence: 99%

π-Conjugated derivatives containing phosphole rings: synthesis, properties and coordination chemistry

Hissler¹,

Lescop²,

Réau³

2005

Comptes Rendus. Chimie

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Structure−Property Relationships in Phosphole-Containing π-Conjugated Systems: A Quantum Chemical Study

Cited by 55 publications

References 24 publications

How to Build Fully π‐Conjugated Architectures with Thienylene and Phenylene Fragments

How to Build Fully π‐Conjugated Architectures with Thienylene and Phenylene Fragments

Comparative Study on the Structural, Optical, and Electrochemical Properties of Bithiophene‐Fused Benzo[c]phospholes

π-Conjugated derivatives containing phosphole rings: synthesis, properties and coordination chemistry

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