Influence of building block aromaticity in the determination of electronic properties of five-membered heterocyclic oligomers

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

doi:10.1039/b109008a

Cited by 71 publications

(52 citation statements)

References 43 publications

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“…Their band gap is predicted to be much lower than in polypyrroles or polythiophenes, for example 1.49 eV for polyphosphole [306] versus 2.0 eV for polythiophene in the first study. Even lower values (1.2 [307] and 1.08 eV [308] ) have been computed in the other studies. The relative lack of aromaticity in phospholes means that their p electrons are not confined within the rings, thus allowing a better delocalization along the polymer backbone than in the case of polypyrroles and polythiophenes.…”

Section: Molecular Materialsmentioning

confidence: 59%

“…[305] The initiator (CH 3 OTf (OTf = CF 3 SO 3 ) or CH 3 I) initially gives a phosphiranium salt which is then attacked by the phosphorus [ 351] By analogy with the thoroughly investigated polypyrroles and polythiophenes which provide very interesting n-or pdoped electroconducting organic materials, it is tempting to investigate the synthesis of polyphospholes. Several recent DFT studies [306][307][308] have demonstrated that a-connected polyphospholes should be good substrates for making efficient organic conductors. Their band gap is predicted to be much lower than in polypyrroles or polythiophenes, for example 1.49 eV for polyphosphole [306] versus 2.0 eV for polythiophene in the first study.…”

Section: Molecular Materialsmentioning

confidence: 99%

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Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

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Section: Molecular Materialsmentioning

confidence: 59%

Section: Molecular Materialsmentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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“…E 00 (᭺), E vert (~), obtained from Equations 2a and 6. TD-DFT B3 LYP/SV(P) calculations of E vert (᭛, [111]). Solid lines are Kuhn fits to the experimental and calculated values.…”

Section: Ab Initio Hartree-fock Rcismentioning

confidence: 99%

“…15), nPs (Fig. 17), [108] nTVs [109] or oligoacenes [110] with standard DFT approaches cannot therefore be accessed, whatever the functional (B3LYP, [19,30,[34][35][36][111][112][113][114] BP86, [34,110] B3P86-30 %, [5,36] BLYP, [34,110] SVMN, [19] PB1PBE, [19] LSDA [36] ) or the basis set. [34] Hybrid methods in which the TD-DFT formalism is applied to ground-state geometries optimized at the Hartree-Fock level lead to an overall shift of the calculated transition energies [39] while keeping the overestimated slope in the 1/N representation.…”

Section: Time-dependent Density Functional Theorymentioning

confidence: 99%

Optical Bandgaps of π‐Conjugated Organic Materials at the Polymer Limit: Experiment and Theory

2007

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In this Review, the extreme care that must be taken when predicting the optical properties of conjugated polymers via the oligomer approach, and when comparing theoretical and experimental data, is illustrated. In the first part, conceptual strategies for the correct determination of optical transitions from experimental spectra and relevant extrapolation procedures at the polymer limit are introduced. The impact of conformational, substitution, solvent, and solid‐state effects on the optical properties is discussed in light of experimental data reported for molecular backbones based on phenylene, phenylenevinylene, and thiophene repeat units. A comparison is then made between experimental results and those provided by standard quantum‐chemical methods, to assess their reliability.

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“…The experimentally determined optical HOMO-LUMO gap of 17 (2.21 eV) is much smaller than that of the phenyl-capped terthiophene (2.85 eV), [22] in good accordance with the theoretical prediction for α,α′-linked oligoheterole models. [23] These results encouraged us to synthesize new α,α′-linked polyphospholes (Section 2.3).…”

Section: Titanacycle-mediated Synthesis Of 25-π-conjugated Phospholementioning

confidence: 99%

Synthesis and Structure-Property Relationships of Phosphole-Based π Systems and Their Applications in Organic Solar Cells

Matano

2015

The Chemical Record

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Phosphole is a chemically tunable heterole, and its π-conjugated derivatives are potential candidates for optoelectronic materials. This account describes recent developments in the synthesis and structure-property relationships of π-conjugated phosphole derivatives made by my research group. Thiophene-phosphole-styrene, phosphole-acetylene-arene, oligophosphole, polyphosphole, areno[c]phosphole, and phosphole-heterole π systems are synthesized using titanacycle-mediated metathesis and palladium-catalyzed cross-coupling reactions. The structural, optical, and electrochemical properties of selected compounds are discussed. Initial results on some applications of thiophene-phosphole copolymers, acenaphtho[c]phospholes, and amine-terthiophene-phosphole donor-π-acceptor dyes in organic solar cells are described. These results give valuable information and guidelines for designing new phosphorus-containing organic materials for molecular electronics.

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Influence of building block aromaticity in the determination of electronic properties of five-membered heterocyclic oligomers

Cited by 71 publications

References 43 publications

Phospha‐Organic Chemistry: Panorama and Perspectives

Phospha‐Organic Chemistry: Panorama and Perspectives

Optical Bandgaps of π‐Conjugated Organic Materials at the Polymer Limit: Experiment and Theory

Synthesis and Structure-Property Relationships of Phosphole-Based π Systems and Their Applications in Organic Solar Cells

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