6H-[1,2,5]Thiadiazolo[3,4-e]thieno[3,2-b]indole-flanked para-azaquinodimethane based aromatic-quinoidal polymer semiconductors with high molecular weights synthesized via direct arylation polycondensation

Xiao, Yufa; Fu, Huaijie; Li, Zefeng; Zheng, Yingxuan; Deng, Ping; Lei, Yanlian; Yu, Yi

doi:10.1039/d3ma00037k

Cited by 6 publications

(3 citation statements)

References 56 publications

(114 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The molar extinction coefficient of AQM3 was almost three times that of AQM1. Nevertheless, it was much lower than 6H-[1,2,5]thiadiazolo [3,4-e]thieno [3,2-b]indole flanked para-azaquinodimethane reported in the literature by Yu et al (170,000 L mol −1 cm −1 ) [39]. The optical band gaps were calculated from the onset of absorption at a maximum wavelength in solution.…”

Section: Optical and Electrochemical Propertiesmentioning

confidence: 83%

New Quinoid Bio-Inspired Materials Using Para-Azaquinodimethane Moiety

Zwaihed,

Maurel,

Kobeissi

et al. 2023

Molecules

View full text Add to dashboard Cite

Quinoid single molecules are regarded as promising materials for electronic applications due to their tunable chemical structure-driven properties. A series of three single bio-inspired quinoid materials containing para-azaquinodimethane (p-AQM) moiety were designed, synthesized and characterized. AQM1, AQM2 and AQM3, prepared using aldehydes derived from almonds, corncobs and cinnamon, respectively, were studied as promising quinoid materials for optoelectronic applications. The significance of facile synthetic procedures is highlighted through a straightforward two-step synthesis, using Knoevenagel condensation. The synthesized molecules showed molar extinction coefficients of 22,000, 32,000 and 61,000 L mol−1 cm−1, respectively, for AQM1, AQM2 and AQM3. The HOMO-LUMO energy gaps were calculated experimentally, theoretically showing the same trends: AQM3 < AQM2 < AQM1. The role of the aryl substituent was studied and showed an impact on the electronic properties. DFT calculations show planar structures with quinoidal bond length alternation, in agreement with the experimental results. Finally, these bio-based materials showed high thermal stabilities between 290 °C and 340 °C and a glassy behavior after the first heating–cooling scan. These results highlight these bio-based single molecules as potential candidates for electronic or biomedical applications.

show abstract

Section: Optical and Electrochemical Propertiesmentioning

confidence: 83%

New Quinoid Bio-Inspired Materials Using Para-Azaquinodimethane Moiety

Zwaihed,

Maurel,

Kobeissi

et al. 2023

Molecules

View full text Add to dashboard Cite

show abstract

“…As research into the structure–morphology–performance relationships of these polymers has advanced, new conjugated polymers with desirable band gaps and exceptional charge transport properties have been discovered using rational Q-D-A design principles. Such advances have inspired follow-up efforts that couple AQM units with specifically designed electroactive units and side chains to produce functional polymers with tunable optical, electronic, and mechanical properties for uses in flexible electronics, OFETs, , organic photovoltaics, , and NIR bioimaging. , …”

Section: Summary and Outlookmentioning

confidence: 99%

p-Azaquinodimethane: A Versatile Quinoidal Moiety for Functional Materials Discovery

2023

View full text Add to dashboard Cite

Conspectus The past 50 years of discovery in organic electronics have been driven in large part by the donor–acceptor design principle, wherein electron-rich and electron-poor units are assembled in conjugation with each other to produce small band gap materials. While the utility of this design strategy is undoubtable, it has been largely exhausted as a frontier of new avenues to produce and tune novel functional materials to meet the needs of the ever-increasing world of organic electronics applications. Its sister strategy of joining quinoidal and aromatic groups in conjugation has, by comparison, received much less attention, to a great extent due to the categorically poor stability of quinoidal conjugated motifs. In 2017 though, the p-azaquinodimethane (AQM) motif was first unveiled, which showed a remarkable level of stability despite being a close structural analogue to p-quinodimethane, a notably reactive compound. In contrast, dialkoxy AQM small molecules and polymers are stable even under harsh conditions and could thus be incorporated into conjugated polymers. When polymerized with aromatic subunits, these AQM-based polymers show notably reduced band gaps that follow reversed structure–property trends to some of their donor–acceptor polymer counterparts and yield organic field-effect transistor (OFET) hole mobilities above 5 cm2 V–1 s–1. Additionally, in an ongoing study, these AQM-based compounds are also showing promise as singlet fission (SF) active materials due to their mild diradicaloid character. An expanded world of AQMs was accessed through their ditriflate derivatives, which were first used to produce ionic AQMs (iAQMs) sporting two directly attached cationic groups that significantly affect the AQM motif’s electronics, producing strongly electron-withdrawing quinoidal building blocks. Conjugated polyelectrolytes (CPEs) created with these iAQM building blocks exhibit optical band gaps stretching into the near-infrared I (NIR-I) region and showed exemplary behavior as photothermal therapy agents. In contrast to these stable AQM examples, the synthetic exploration of AQMs also produced examples of more typical diradicaloid reactivity but in forms that were controllable and produced intriguing and high-value products. With certain substitution patterns, AQMs were found to dimerize to form highly substituted [2.2]paracyclophanes in distinctly more appreciable yields than typical cyclophane formation reactions. Certain AQM ditriflates, when crystallized, undergo light-induced topochemical polymerization to form ultrahigh molecular weight (>106 Da) polymers that showed excellent performances as dielectric energy storage materials. These same AQM ditriflates could be used to produce the strongly electron-donating redox-active pentacyclic structure: pyrazino[2,3-b:5,6-b′]diindolizine (PDIz). The PDIz motif allowed for the synthesis of exceedingly small band gap (0.7 eV) polymers with absorbances reaching all the way into the NIR-II region that were also found to produce strong photothermal effects...

show abstract

“…Due to the high stability, this moiety has been connected with various aromatic subunits and developed several small molecules and polymers (Chart ). − The developed compounds have been found to show notably reduced band gaps and high carrier mobility and singlet fission characteristics. Interestingly, none of the compounds have been reported to be fluorescent.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of p-Azaquinodimethane-based Quinoidal Fluorophores

2023

J. Org. Chem.

View full text Add to dashboard Cite

Quinoidal π-conjugated systems are sought-after materials for semiconducting applications because of their rich optical and electronic characteristics. However, the analogous fluorescent compounds are extremely rare, with just two reports in the literature. Here, we present the design and development of a third series of quinoidal fluorophores [(2,5-diarylidene)-3,6-bis(hexyloxy)-2,5-dihydropyrazine (Q1–Q5)] that incorporates p-azaquinodimethane. The fluorophores are synthesized in a two-step synthetic approach employing Knoevenagel condensation of N,N-diacetyl-piperazine-2,5-dione with different aromatic aldehydes followed by O-alkylation in high yields. Q1–Q5 are strongly emissive, and by altering the aryl-substituents, the emission colors can be modulated from blue to orange. The compounds possess emission maxima (λem) at 475–555 nm in the solution state and 510–610 nm in the solid state, with fluorescence quantum yields of up to 60%. To the best of our knowledge, the reported systems are the first quinoidal dual-state emissive (solution- and solid-state) compounds. In trifluoroacetic acid, Q5 exhibits halochromic behavior, with a dramatic color change from yellow to blue. Furthermore, the preliminary fluorescent sensing studies demonstrated that Q5 could act as a selective turn-off fluorescence probe for electron-deficient picric acid (PA), with an emission quenching of >90% in the solution state. The thin-layer chromatography (TLC) strip sensor of Q5 was also designed to detect PA in water.

show abstract

6H-[1,2,5]Thiadiazolo[3,4-e]thieno[3,2-b]indole-flanked para-azaquinodimethane based aromatic-quinoidal polymer semiconductors with high molecular weights synthesized via direct arylation polycondensation

Cited by 6 publications

References 56 publications

New Quinoid Bio-Inspired Materials Using Para-Azaquinodimethane Moiety

New Quinoid Bio-Inspired Materials Using Para-Azaquinodimethane Moiety

p-Azaquinodimethane: A Versatile Quinoidal Moiety for Functional Materials Discovery

Synthesis of p-Azaquinodimethane-based Quinoidal Fluorophores

Contact Info

Product

Resources

About