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Presented here is the design, synthesis, and study of a variety of novel hydrogen-bonding-capable π-conjugatedN-heteroacenes, 1,4-dihydropyrazino[2,3-b]quinoxaline-2,3-diones (DPQDs). The DPQDs were accessed from the corresponding weakly hydrogen-bonding dicyanopyrazinoquinoxaline (DCPQ) suspensions with excess potassium hydroxide, resulting in moderate to good yields. Both families of compounds were analyzed by UV–vis and NMR spectroscopy, where the consequences of hydrogen bonding capability could be assessed through the structure–property studies. Conversion of the DCPQs into hydrogen-bonding capable DPQDs results in modulation of frontier MO energies, higher molar extinction coefficients, enhanced crystallinity, and on-average higher thermal stability (where in some cases the 5% weight loss temperature is increased by up to 100 °C). Single crystal X-ray diffraction data could be obtained for three DPQDs. One reveals pairwise hydrogen bonding in the solid state as well as a herringbone packing arrangement rendering it a promising candidate for additional studies in the context of organic optoelectronic devices.
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Structure–Assembly–Property Relationships of Simple Ditopic Hydrogen-Bonding-Capable π-Conjugated Oligomers
A series of simple ditopic hydrogen-bonding-capable molecules functionalized with 2,4-diamino-1,3,5-triazine (DAT), barbiturate (B), and phthalhydrazide (PH) on both termini of a 2,2′-bithiophene linker were designed and synthesized. The intrinsic electronic structures of the ditopic DAT, PH, and B molecules were investigated with ground-state density functional theory calculations. Their solution absorbance was investigated with UV-vis, where it was found that increasing size of R group substituents on the bithiophene linker resulted in a general blue-shift in solution absorbance maximum. The solid-state optical properties of ditopic DAT and B thin films were evaluated by UV-vis, and it was found that the solid-state absorbance was red-shifted with respect to solution absorbance in all cases. The three DAT molecules were vacuum-thermal-deposited onto Au(111) substrates and the morphologies were examined using scanning tunneling microscopy. (DAT-T)2 was observed to organize into six-membered rosettes on the surface, whereas (DAT-TMe)2 formed linear assemblies before and after thermal annealing. For (DAT-Toct)2 , an irregular arrangement was observed, while (B-TMe)2 showed several co-existent assembly patterns. The work presented here provides fundamental molecular–supramolecular relationships useful for semiconductive materials design based on ditopic hydrogen-bonding-capable building blocks.
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- Award ID(s):
- 1904534
- PAR ID:
- 10284827
- Date Published:
- Journal Name:
- Organic Materials
- Volume:
- 03
- Issue:
- 02
- ISSN:
- 2625-1825
- Page Range / eLocation ID:
- 302 to 316
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1055/a-1534-1508
