Comparison of CC Triple and Double Bonds as Spacers in Push–Pull Chromophores

Frank, Brigitta; Laporta, Philip R.; Breiten, Benjamin; Kuzyk, Mark C.; Jarowski, Peter D.; Schweizer, W. Bernd; Seiler, Paul; Biaggio, Ivan; Boudon, Corinne; Gisselbrecht, Jean‐Paul; Diederich, François

doi:10.1002/ejoc.201100378

Cited by 34 publications

(36 citation statements)

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“…The role of the acetylenic groups as spacers in push–pull chromophores has been comprehensively studied for donor‐substituted cyanoethynylethenes (CEEs) 9. 38, 39 The introduction of alkynyl spacers ( n =0–3) in these chromophores resulted in less readily homogeneous solutions due to the resulting planar molecular geometry and concomitant low solubility 39. Also, there were indications that saturation of the third‐order polarizability could already be reached at the diyne stage, but the weak solubility did not allow a full characterization 39.…”

Section: Introductionmentioning

confidence: 99%

“…38, 39 The introduction of alkynyl spacers ( n =0–3) in these chromophores resulted in less readily homogeneous solutions due to the resulting planar molecular geometry and concomitant low solubility 39. Also, there were indications that saturation of the third‐order polarizability could already be reached at the diyne stage, but the weak solubility did not allow a full characterization 39. On the other hand, a donor‐substituted TCBD with a five‐triple‐bond spacer displayed good solubility and showed a very strong third‐order optical nonlinearity for self‐phase modulation at a wavelength 1.5 μm, which suggested a high potential for NLO applications of alkyne spacers in suitably designed chromophores 40…”

Section: Introductionmentioning

confidence: 99%

“…[39] Also, there were indications that saturation of the third-order polarizability could already be reached at the diyne stage, but the weak solubility did not allow a full char-acterization. [39] On the other hand, a donor-substituted TCBD with a five-triple-bond spacer displayed good solubility and showed a very strong third-order optical nonlinearity for self-phase modulation at a wavelength 1.5 mm, which suggested a high potential for NLO applications of alkyne spacers in suitably designed chromophores. [40] In this work, we present a systematic study on the influence of the acetylene spacer length in TCBD-derived pushpull chromophores.…”

Section: Introductionmentioning

confidence: 99%

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Donor–Acceptor (D–A)‐Substituted Polyyne Chromophores: Modulation of Their Optoelectronic Properties by Varying the Length of the Acetylene Spacer

Štefko

Tzirakis

Breiten

et al. 2013

Chemistry A European J

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A series of donor-acceptor-substituted alkynes, 2 a-f, was synthesized in which the length of the π-conjugated polyyne spacer between the N,N-diisopropylanilino donor and the 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) acceptor was systematically changed. The effect of this structural change on the optoelectronic properties of the molecules and, ultimately, their third-order optical nonlinearity was comprehensively investigated. The branched N,N-diisopropyl groups on the anilino donor moieties combined with the nonplanar geometry of 2 a-f imparted exceptionally high solubility to these chromophores. This important property allowed for performing INADEQUATE NMR measurements without (13) C labeling, which, in turn, resulted in a complete assignment of the carbon skeleton in chromophores 2 a-f and the determination of the (13) C-(13) C coupling constants. This body of data provided unprecedented insight into characteristic (13) C chemical shift patterns in push-pull-substituted polyynes. Electrochemical and UV/Vis spectroscopic studies showed that the HOMO-LUMO energy gap decreases with increasing length of the polyyne spacer, while this effect levels off for spacers with more than four acetylene units. The third-order optical nonlinearity of this series of molecules was determined by measuring the rotational averages of the third-order polarizabilities (γrot ) by degenerate four-wave mixing (DFWM). These latter studies revealed high third-order optical nonlinearities for the new chromophores; most importantly, they provided fundamental insight into the effect of the conjugated spacer length in D-A polyynes, that can be exploited in the future design of suitable charge-transfer chromophores for applications in optoelectronic devices.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Donor–Acceptor (D–A)‐Substituted Polyyne Chromophores: Modulation of Their Optoelectronic Properties by Varying the Length of the Acetylene Spacer

Štefko

Tzirakis

Breiten

et al. 2013

Chemistry A European J

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“…With a linear structure and extensive π‐electron delocalization, polyynes represent intriguing organic compounds for third‐order nonlinear optical applications . In one study, the electronic contribution to the second hyperpolarizabilities ( γ ele ) of triisopropylsilyl endcapped polyynes ( TIPS[ n ] , Fig.…”

Section: Introductionmentioning

confidence: 99%

Absolute Raman intensity measurements and determination of the vibrational second hyperpolarizability of adamantyl endcapped polyynes

Lucotti

Tommasini

Fazzi

et al. 2012

J Raman Spectroscopy

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Linear sp‐carbon polyynes are ideal molecules for the direct investigation of the physical properties of one‐dimensional conjugated systems. Traditionally, the main obstacle to the study of these systems has been their instability under normal laboratory conditions. Thanks to improved chemical syntheses, a broadened range of polyynes is now available for study, including the hydrocarbon series endcapped with adamantyl groups, Ad[n]. In this work, the quantitative Raman spectroscopic analysis is reported for each member of this homologous series. The Raman scattering intensities corresponding to the major features of the polyyne segment (i.e., the effective conjugation coordinate or Я lines) are then used to evaluate the nonlinear optical (NLO) behavior via determination of the vibrational contribution to the second hyperpolarizability (γvib). This study shows that γvib values as a function of length are of the same order of magnitude as those arising from the electronic contribution to the molecular second hyperpolarizability, γele, as reported for triisopropylsilyl polyynes, TIPS[n], using the differential optical Kerr effect technique. The nonlinear response for Ad[n] polyynes, supported by the analogous response for TIPS[n] polyynes, confirms that linear sp‐carbon molecules have large second hyperpolarizabilities that show a power‐law increase in γ‐values versus length that is larger than other known π‐conjugated systems, such as polyenes. Furthermore, the NLO response of polyynes versus length approaches the theoretical limit described by Kuzyk more closely than other conjugated organic oligomers. Copyright © 2012 John Wiley & Sons, Ltd.

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“…The instrument is equipped with a nitrogen laser (λ = 337 nm) and was operated at the following parameters: averaged singleshot spectra 200, laser pulse repetition rate 9.0 Hz, delay time 200 ns (pulsed ion extraction). According to the instrument setup, which is explained in further detail by Ómarsson et al, 40 the following acceleration voltages were chosen: 20.00 (ion source 1), 16.60 (ion source 2 in reflectron mode), 18.50 (ion source 2 in linear mode), and 23.0 kV (linear-field reflectron). 40,41 The mass calibration was conducted with CsI clusters (generated from CsI 3 ).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Laser Desorption Mass Spectrometry of End Group-Protected Linear Polyynes: Evidence of Laser-Induced Cross-Linking

et al. 2015

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End group-protected linear polyynes of composition Tr*−(CC) n −Tr* (with Tr* representing the super trityl group and n = 2, 4, 6, 8, 10) and tBu−(CC) 6 − tBu (with tBu being the tertiary butyl group) have been studied by laser desorption ionization (LDI) time-of-flight (ToF) mass spectrometry. tBu-terminated polyyne molecules show considerably higher stability during laser activation than Tr*-end-capped polyyne molecules. A key feature is the abundant formation of oligomeric species upon laser activation. Tandem mass spectrometry reveals strong bonding within the oligomers which indicates cross-linking of the former polyynes within the oligomers. The process is more abundantly occurring and less energy demanding than the laser-induced coalescence of C 60 . Cross-linking is more efficient with the smaller end group (tBu), and larger oligomers are formed when the chain length of the polyyne increases, both a result of enhanced interaction of the triple bonds in neighboring chains. The presence of the matrix molecules in matrix-assisted (MA)LDI hinders the polyyne interaction, and oligomer formation is markedly reduced.

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Comparison of CC Triple and Double Bonds as Spacers in Push–Pull Chromophores

Cited by 34 publications

References 56 publications

Donor–Acceptor (D–A)‐Substituted Polyyne Chromophores: Modulation of Their Optoelectronic Properties by Varying the Length of the Acetylene Spacer

Donor–Acceptor (D–A)‐Substituted Polyyne Chromophores: Modulation of Their Optoelectronic Properties by Varying the Length of the Acetylene Spacer

Absolute Raman intensity measurements and determination of the vibrational second hyperpolarizability of adamantyl endcapped polyynes

Laser Desorption Mass Spectrometry of End Group-Protected Linear Polyynes: Evidence of Laser-Induced Cross-Linking

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