Self-Assembly of Pyrazine-Containing Tetrachloroacenes

Jang, Kyoungmi; Brownell, Lacie V.; Forster, Paul M.; Lee, Dong‐Chan

doi:10.1021/la203623s

Cited by 22 publications

(15 citation statements)

References 42 publications

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“…37−40 We anticipated that including dialkoxyphenazine in the title compounds would facilitate organogelation, as dialkoxyphenazine has been known to be an efficient gelator. 41−43 When comparing the title compounds, the pendant in BTD-P is the only unit without an alkyl group which would not interfere with fibrillation driven by dialkoxyphenzaine. The remaining compounds contain alkyl side groups on the pendants, and it is unclear if the alkyl side groups on the pendants support or interfere with fibrillation.…”

Section: Results and Discussionmentioning

confidence: 99%

Understanding the Electronic Properties of Acceptor–Acceptor′–Acceptor Triads

et al. 2019

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In order to develop new organic materials for optoelectronic applications, a fundamental understanding of the electronic properties of specific chromophore combinations must be realized. To that end, we report “model” acceptor (A)–acceptor′ (A′)–acceptor (A) triads in which the pendants (A′) we selected are well-known components of organic optoelectronic applications. Our pendants are sandwiched between two dialkoxyphenazine (A) through an alkyne bond. The A′ was systematically increased in electron-deficiency from benzothiadiazole ( BTD-P ) to naphthalene diimide with octyl ( NDI-O-P ) or ethylhexyl groups ( NDI-EH-P ) to perylene diimide with ethylhexyl ( PTCDI-EH-P ) to assess changes in the electronic properties of the resultant molecules. Characterizations were performed using both experimental and theoretical methods. From optical and cyclic voltammetry, we found that the electron deficiency of each pendant was directly correlated to the energy level of the lowest unoccupied molecular orbital ( E LUMO ). When examining the simple molecular orbital diagrams produced at the B3LYP/6-31G* level of theory, the LUMOs were, as expected, primarily localized on the more electron-deficient pendants. In terms of the energy level of the highest occupied molecular orbital ( E HOMO ), the numerical values obtained experimentally also correlated with values obtained computationally. Attempting to construct a simplified model that would explain these correlated values was not as readily apparent, given the disparate physical characteristics of these compounds. For example, BTD-P and NDI-O-P/NDI-EH-P achieved planarity when computationally optimized, but PTCDI-EH-P adapted a “buckled” geometry on the central PTCDI, consequently forcing the attached phenazines out-of-plane. The title compounds showed solvent polarity-dependent fluorescence, which is indicative of intramolecular charge transfer. In conjunction with our theoretical study, the current system can be viewed as an extension of donor–acceptor–donor systems. Thermal properties characterized by differential scanning calorimetry revealed that reversible phase transitions were only observed for BTD-P . In addition, BTD-P was found to be an efficient gelator in 1,1,1-trichloroethane and toluene. The other compounds in this study did not form gels in any of the solvents tested, which may have been a result of the alkyl groups on the pendants hampering the fibrillation process.

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Section: Results and Discussionmentioning

confidence: 99%

Understanding the Electronic Properties of Acceptor–Acceptor′–Acceptor Triads

et al. 2019

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“…Generally, nanofibers are taken as an intermediate state between molecularly dissolved species and organogels upon increasing the concentration. 42 The strong tendency of 1(m) to self-assemble into nanofibers inspired us to investigate their gelation capability. It is known that gelation behavior of a compound is strikingly dependent on its inherent properties, solvent, temperature, concentration, cooling rate, etc.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and self-assembly of tetraphenylethene and biphenyl based AIE-active triazoles

et al. 2012

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Self-assembly of fluorescent functional materials has attracted increasing interest in the fabrication of optoelectronic and biological nanodevices. Tetraphenylethene (TPE) is a typical dye molecule with aggregation-induced-emission (AIE) characteristics. Melding TPE carrying triple-bond functionality with diazide-containing biphenyl through ''click'' chemistry generates AIE-active luminogens [1,1 0biphenyl]-4,4 0 -diyl bis(6-(4-(4-(1,2,2-triphenylvinyl)phenyl)-1H-1,2,3-triazol-1-yl) hexanoate) [1(5)] and [1,1 0 -biphenyl]-4,4 0 -diyl bis(11-(4-(4-(1,2,2-triphenylvinyl)phenyl)-1H-1,2,3-triazol-1-yl) undecanoate) [1(10)] with solid state efficiencies up to unity. Slow addition of dilute THF solutions of 1(m) (m ¼ 5, 10) into nonsolvents such as n-hexane and water yields self-assembled white wooly solids. TEM and SEM observations reveal the (helical) nanofibrous structure of the aggregates. Upon cooling from their concentrated hot solutions, 1(m) readily precipitate. Meanwhile, they can also form gels at high concentrations. Both precipitates and gels of 1(m) exhibit structures similar to those of the aggregates formed in nonsolvents. These results indicate that 1(m) can facilely self-assemble into high emission efficiency (helical) nanofibers, thus paving the way for their optoelectronic and biological applications.Chart 1 Chemical structure of 1(m) (m ¼ 5, 10).Scheme 1 Synthetic route to 1(m) (m ¼ 5, 10).

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“…Ariga, Hill, and co‐workers have reviewed the self‐assembly and solid‐state structures of some long‐chain alkoxy‐substituted larger heteroacenes 4d. Very recently Lee and co‐workers investigated the self‐assembly of 74 a – c ; These form gels with attractive structures from different organic solvents, as shown for 74 c in Figure 10 48…”

Section: Structures and Supramolecular Orderingmentioning

confidence: 99%

“… Self‐assembly (left) and structure (right) of 74 . SEM micrograph reproduced with permission from the American Chemical society 48. Scale bar=1 μm.…”

Section: Structures and Supramolecular Orderingmentioning

confidence: 99%