Photorefractive hyper-structured molecular glasses constructed by calix[4]resorcinarene core and carbazole-based methine nonlinear optical chromophore

Abstract

Seven C-methylcalix[4]resorcinarene (CRA)-based photorefractive (PR) hyper-structured molecular glasses (HSMGs) containing carbazole-based methine nonlinear optical (NLO) chromophores were designed and synthesized via esterification between carboxyl-containing asymmetric CRA core molecule and hydroxyl-containing functional compounds. When the feed ratio of hydroxyl-containing NLO functional compounds to carboxyl groups of CRA-COOH was kept at 1.5/1 by mole, the degree of introduction of NLO chromophore to the CRA core was above 70%. All the HSMGs show low glass transition temperatures (Tg), and good solubility in common low boiling point solvents such as THF, CHCl3, etc. Powder XRD and UV-vis absorption in films of HSMGs indicate that the aggregation, packing and crystallization of the NLO chromophores in these HSMGs had been effectively reduced. Doping with Nethyl-carbazole (ECz) as a plasticizer and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as a photosensitizer, all the HSMGs composites showed good PR effects. All the coupling gain coefficients (Γ) of HSMGs-based composites are about twice to the corresponding small molecular NLO chromophores-based composites, thanks to the decreased NLO chromophores antiparallel packing caused by the asymmetric CRA core. Among them, CRA-CSN/ECz/PCBM (69:30:1, wt.%) composite exhibited the best performance with the Γ value of 78.2 cm-1 at the external electric field of 12.5 V μm-1 , which is one of the best performance in molecular glasses under the same test conditions. Coupled with their convenient synthesis, this work will provide a new simple design strategy for organic PR materials.

Graphitic nanosheets via two-dimensional polymerization enhancing organic all-optically controlled photorefractive performance

“…5b. The result indicated the all the photorefractive devices have an excellent optical transmittance due to the glassy morphology of organic photorefractive compound CRA-CSN 75 -Cz 25 [53], which is an necessary condition to form the photorefractive grating inside organic photorefractive composites.…”

“…The coupling gain coefficient (Γ) in the AOC-PR photorefractive devices is measured to be 80.1 cm −1 by the two-beam coupling (TBC) experiments under zero external electric field through the externally and internally plasticizing optimization of AOC-PR performance [53]. The chemical structures of CRA-CSN 75 -Cz 25 , ECZ and PC 61 BM are shown in Fig.…”

Host–Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides: An Experimental–Computational Analysis of the Guest Inclusion Properties

“…This in turn has led to exotic materials with tunable chemical and physical properties . Functionalized resorcinarenes have found use in nanoparticle synthesis, − optical , and chemosensors, gels, and separation applications . In addition to the various potential applications of resorcinarenes, their use in rigorous quantitative H-G studies to extrapolate structure–property relationships and gain insights into fundamental principles, e.g., guest binding affinities, size and shape, and conformational flexibility has always received wide attention in supramolecular chemistry research .…”

Stabilization of Intrinsic Ions in Perovskite Solar Cells by Employment of a Bipolar Star-Shaped Organic Molecule as a Charge Transport Buffer

“…However, we need electron donors and electron acceptors to be present in one compound simultaneously to cope with excess electrons and holes. Therefore, a bipolar-transporting star-shaped organic molecule named core calix[4]­resorcinarene (CRA)–triphenylamine (TPA) has been designed based on our previous work (see the Supporting Information for details on the synthesis). , Such organic molecules can contain both electron donors and electron acceptors, which can be a good adjust buffer for charge transport. The space charge-limited-current (SCLC) measurement shows that the value of the defect density has been decreased to ≈1/4 after doping CRA–TPA in the perovskite film.…”