An official website of the United States government
Fluorinated triphenylenes and a path to short tailed discotic liquid crystals: synthesis, structure and transport properties
A new synthetic approach for fluorinated alkoxytriphenylene discotic liquid crystals is presented. This methodology exploits the previously described photocyclodehydrofluorination (PCDHF) reaction for the preparation of fluorinated triphenylene derivatives coupled with a variety of nucleophilic aromatic substitution (S N Ar) reactions. This particular combination of reactions provides a versatile route to discotic materials with carefully controlled core fluorine and alkoxy tail content. In the course of these studies, new discotic materials with minimal tail content have been revealed. The mesogenic properties of these materials are reported, and their charge transport properties are measured using the time of flight technique.
more »
« less
- Award ID(s):
- 1809536
- PAR ID:
- 10407397
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 3
- Issue:
- 1
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 534 to 546
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Recently, a large family of at least 14 discotic liquid crystals was discovered that are exceptions to the conventional paradigm that discotic mesogens tend to feature long, flexible tails on their periphery. To understand why these materials are liquid crystals, as well as the structural determinants of discotic phase behavior, we studied a group of closely related small tail-free disk-like molecules, including both mesogenic and non-mesogenic compounds differing only in the position of a single fluorine substituent. The rigidity and structural simplicity of these molecules make them well suited to for study by large, fully all-atom simulations. Using a combination of static and dynamic metrics, we were able to identify several key features of the columnar mesophase and, thereby, conclusively identify a columnar liquid crystalline mesophase present in a subset of our systems. Our simulations feature molecules hopping between columns in the columnar mesophase and distinctive molecular rotations in 60° steps about the columnar axis. The ability to create and characterize columnar mesophases in silico provides a potent tool for untangling the structural determinants of liquid crystalline behavior in these and other tail-free discotic liquid crystals.more » « less
-
Abstract Hypergolic reactions have emerged as a new synthetic approach enabling the rapid production of a diverse set of materials at ambient conditions. While hypergolic reactions bear several similarities to the well-established flame spray pyrolysis (FSP), the former has only recently been demonstrated as a viable approach to materials synthesis. Here we demonstrate a new pathway to 2D materials using hypergolic reactions and expand the gallery of nanomaterials synthesized hypergolically. More specifically, we demonstrate that ammonia borane complex, NH3BH3, or 4-fluoroaniline can react hypergolically with fuming nitric acid to form hexagonal boron nitride/fluorinated carbon nanosheets, respectively. Structural and chemical features were confirmed with x-ray diffraction, infrared, Raman, XPS spectroscopies and N2porosimetry measurements. Electron microscopy (SEM and TEM) along with atomic force microscopy (AFM) were used to characterize the morphology of the materials. Finally, we applied Hansen affinity parameters to quantify the surface/interfacial properties using their dispersibility in solvents. Of the solvents tested, ethylene glycol and ethanol exhibited the most stable dispersions of hexagonal boron nitride (h-BN). With respect to fluorinated carbon (FC) nanosheets, the suitable solvents for high stability dispersions were dimethylsulfoxide and 2-propanol. The dispersibility was quantified in terms of Hansen affinity parameters (δd,δp,δh) = (16.6, 8.2, 21.3) and (17.4, 10.1, 14.5) MPa1/2for h-BN and FC, respectively.more » « less
-
Abstract Four extensively fluorinated tetraphenylethylenes (TPE) and one extensively fluorinated triphenylethylene have been synthesized using combinations of copper‐catalyzed C−H functionalization reactions and Stille coupling reactions. Surprisingly, in contrast to the parent TPE, these compounds show little to no aggregation‐induced emission (AIE). Instead, photocyclization into fluorinated phenanthrene products occurs. Effects of solvent and oxygen on the yield and selectivity of this photocyclization have been examined.more » « less
-
1-Amino-1-hydrazino-2,2-dinitroethylene (HFOX) is a potential reactive intermediate for a new class of energetic materials. Now we describe its condensation with various carbonyl compounds in the presence of acidic and basic catalysts. Condensation of HFOX with α-diones and β-diones gives products of much interest. α-Diones undergo cyclization in the presence of base to form six-membered ring products, while β-diones cyclize to five-membered ring products in the presence of acid. One of the exciting reactions is the formation of ammonium (5,6-dimethyl-1,2,4-triazin-3-yl)dinitromethanide salt, 5c, which was isolated by using aqueous ammonia as a nucleophilic base. All new compounds were fully characterized by advanced spectroscopic techniques. The structures of 5, 5c, 5e, 9, 11, and 12a are supported by single crystal X-ray diffraction analysis. Most of the new six membered ring compounds have good thermostabilities (>200 °C), while the fluorinated five membered ring compound, 12b, has the highest density of 2.04 g cm −3 at 25 °C. Heats of formation and detonation properties were calculated by using Gaussian 03 and EXPLO5 software programs. Nearly all new compounds have very good detonation properties, especially, triazine salts, 5e ( D v = 7513 m s −1 ; P = 24.45 G P a), and 5f ( D v = 7948 m s −1 ; P = 26.27 G P a) as well as azide derivative 11 ( D v = 8166 m s −1 ; P = 25.48 G P a), which are superior to TNT ( D v = 6824 m s −1 ; P = 19.40 G P a). These findings provide a new perspective for the synthesis of novel high performing energetic materials.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1ma00606a
