Divergent synthesis and optoelectronic properties of oligodiacetylene building blocks

Pilzak, Gregor S.; Lagen, Barend van; Sudhölter, Ernst J. R.; Zuilhof, Han

doi:10.1016/j.tetlet.2008.05.135

Cited by 5 publications

(7 citation statements)

References 13 publications

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“…This observation shows the stabilizing effect of an aromatic solvent on the excited state of these molecules. This red shift in the maximum absorption resembles those values determined previously for oligodiacetylenes6 and homocoupled oligodiacetylenes8 and is analogous to data reported for shorter diacetylene‐based oligomers 7. 10, 39–41 The shortest ThODA series 1 ‐ n displays similar absorption maxmia in both hexane and methanol.…”

Section: Resultssupporting

confidence: 88%

“…This red shift in the maximum absorption resembles those values determined previously for oligodiacetylenes [6] and homocoupled oligodiacetylenes [8] and is analogous to data reported for shorter diacetylene-based oligomers. [7,10,[39][40][41] The shortest ThODA series 1-n displays similar absorption maxmia in both hexane and methanol. The shift of the maximum absorption peak going from n-hexane to methanol (refractive index = 1.33; E T (30) = 55.4 kcal mol À1 ) [38] for the other oligomers under study is marginal.…”

Section: Steady-state Optical Absorption In Solutionmentioning

confidence: 95%

“…The conjugation in ThODA and HThODA oligomeric chains is therefore not significantly decreased by kinks or torsions in the backbone. [6][7][8] The effective conjugation length (ECL) for these oligomers is therefore at least 20 and most likely > 20 conjugated double and triple bonds.…”

Section: Steady-state Optical Absorption In Solutionmentioning

confidence: 99%

“…[5] Recently, we developed novel methods for the synthesis of oligodiacetylene-based materials that have allowed a detailed photo-physical study that clarified the optical properties of polydiacetylenes. [6][7][8] The development of new oligodiacetylene-based materials is often hampered by their low solubility and a laborious and troublesome synthesis of significantly elongated oligomers. [9,10] Although extensive studies based on oligoenes, [11,12] oligoarylenevinylenes, [13,14] oligotriacetylenes, [15][16][17][18][19][20][21] and oligothiophenes, [22][23][24][25][26][27][28] are known, analogous studies centered around the diacetylene functionality as present in polydiacetylenes are rather scarce.…”

Section: Introductionmentioning

confidence: 99%

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Hybrid Conjugated Organic Oligomers Consisting of Oligodiacetylene and Thiophene Units: Synthesis and Optical Properties

Pilzak

Gruijthuijsen

Doorn

et al. 2009

Chemistry A European J

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Novel and highly soluble hybrid conjugated organic oligomers consisting of oligodiacetylene and thiophene units have been synthesized in high purity through iterative and divergent approaches based on a sequence of Sonogashira reactions. The series of thiophene-containing oligodiacetylenes (ThODAs) and homocoupled ThODAs (HThODAs) show--both in solution and in the solid state--a strong optical absorption, which is progressively red shifted with increasing chain length. The linear correlation of the absorption maximum (lambda(A)(max)) with the inverse of conjugation length (CL = number of double and triple bonds) shows that the effective conjugation length of this system is extended up to at least CL = 20. Furthermore, absorption measurements of dropcast thin films display not only a bathochromic shift of the absorption maxima but also a higher wavelength absorption, which is attributed to increased pi-pi interactions. The wavelength of the maximum fluorescence emission (lambda(E)(max)) also increases with CL, and emission is maximal for oligomers with CL=7-12 (fluorescence quantum yield Phi(F) = approximately 0.2). Both longer and shorter oligomers display marginal emission. The calculated Stokes shifts of these planar materials are relatively large (0.4 eV) for all oligomers, and likely due to excitation to the S(2) state, thus suggesting that the presence of enyne moieties dominates the ordering of the lowest excited states. The fluorescence lifetimes (tau(F)) are short (tau(F,max) =<<1 ns) and closely follow the tendency obtained for the fluorescence quantum yield. The anisotropy lifetimes show a near-linear increase with CL, in line with highly rigid oligomers.

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Section: Resultssupporting

confidence: 88%

Section: Steady-state Optical Absorption In Solutionmentioning

confidence: 95%

Section: Steady-state Optical Absorption In Solutionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Hybrid Conjugated Organic Oligomers Consisting of Oligodiacetylene and Thiophene Units: Synthesis and Optical Properties

Pilzak

Gruijthuijsen

Doorn

et al. 2009

Chemistry A European J

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“…Therefore, in this study, the corresponding charged monodisperse oligodiacetylenes (ODAs) are used as model compounds to determine the evolution of the optoelectronic properties as a function of the conjugation length. The synthesis of the ODA series under study, and their optoelectronic characterization is described by us elsewhere . The ODA series 1 − n is depicted in Figure .…”

Section: Introductionmentioning

confidence: 99%

Radical Cations of All-Trans Oligodiacetylenes: Optical Absorption and Reactivity toward Nucleophiles

et al. 2009

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High yields of the radical cations of oligodiacetylenes have been prepared by photoinduced electron transfer using a positively charged cosensitizer and by pulse radiolysis. The absorption maxima of the oligodiacetylene (ODA) radical cations show a bathochromic shift to the infrared region and a large increase of their lifetimes with chain elongation. Their reactivity toward nucleophiles decreases for longer ODAs, illustrating clearly the stabilizing effect of charge delocalization along the oligomeric chain. This also implies a very low reactivity of ODA radical cations toward trace amounts of water in optoelectronic devices.

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Synthesis and Optoelectronic Properties of Nanometer‐Sized and Highly Soluble Homocoupled Oligodiacetylenes

Pilzak¹,

Baggerman²,

Lagen³

et al. 2009

Chemistry A European J

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A new series of pure, nanometer-sized and highly-soluble homocoupled oligodiacetylenes (HODA) consisting of two symmetrical oligodiacetylene units was synthesized with high yield and on a multi-milligram scale under mild, catalytic Sonogashira conditions. The lambda(max) and the epsilon(max) of absorption for these HODAs show an increase with the chain elongation. The lambda(max) converges to 450 nm for the longest members of the series at micromolar concentration and to 462 nm for thin drop-casted films. An additional red-shifted absorption is observed in the solid state and in solution at low temperatures, which is caused by aggregation. The lambda(max) of the fluorescence emission increases with the chain length and reaches 492 nm for the longest oligomer. The fluorescence quantum yield has its maximum for the shortest oligomer and decreases rapidly for the longer ones. A similar trend is found for the fluorescence lifetime with a maximum of 100 ps for the homocoupled monomer. The rotational correlation time shows a linear increase with the oligomer length. This reveals a significant persistence length and indicates that the HODA molecules are fully stretched molecular rods (up to 8.2 nm).

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Divergent synthesis and optoelectronic properties of oligodiacetylene building blocks

Cited by 5 publications

References 13 publications

Hybrid Conjugated Organic Oligomers Consisting of Oligodiacetylene and Thiophene Units: Synthesis and Optical Properties

Hybrid Conjugated Organic Oligomers Consisting of Oligodiacetylene and Thiophene Units: Synthesis and Optical Properties

Radical Cations of All-Trans Oligodiacetylenes: Optical Absorption and Reactivity toward Nucleophiles

Synthesis and Optoelectronic Properties of Nanometer‐Sized and Highly Soluble Homocoupled Oligodiacetylenes

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