Effects of ortho-Phenyl Substitution on Molecular Arrangements of Octadehydrodibenzo[12]annulene

Abstract

To modulate assembly manners of octadehydrodibenzo [12]annulene ([12]DBA) core in solid state, we first synthesized ortho-phenyl-substituted derivative 2 and investigated the effects of the substituents on the molecular stacking manner of the [12]DBA core.[12]DBA 2 yielded four types of crystals, which differ from that of the parent compound: Namely, the guest-free crystal possessing an offset stacking manner (I-GF), the solvate with a edge-to-face arrangement (II), the solvates with zigzag π-stacked arrangements (III and III¤), and the solvate with 1D π-stacked columnar arrangements (IV). In the crystals, the phenyl groups contribute to limiting the stacking geometry of the [12]DBA cores and to forming void spaces accommodating various guest species, allowing versatile molecular assembly manners hitherto known for [12]DBA derivatives. We revealed that the crystals showed structure dependent fluorescence and charge carrier behaviors.

A Series of Layered Assemblies of Hydrogen-Bonded, Hexagonal Networks of C3-Symmetric π-Conjugated Molecules: A Potential Motif of Porous Organic Materials

“…Remarkably, the DTA curve of T18-1 shows a sharp exothermic peak at 254 °C. Such a sharp exothermic profile is typical for 1,4-diyne contained macrocycles and is ascribable to a thermal reaction, such as random polymerization of the 1,4-butadiyne moieties or graphenization . The resulting black material was again insoluble for common organic solvents.…”

Modulation of Band Gaps toward Varying Conductivities in Heterometallic One-Dimensional Chains by Ligand Alteration and Third Metal Insertion

“…Then, to evaluate a conductive nature of the metal complex wire, measurements with flash-photolysis time-resolved microwave conductivity (TRMC) were conducted, which provides the nanometer-scale photoconductivity of charge carriers generated by laser pulse irradiation under a low-power microwave electric field. − Micrometer-scale crystals were spread on an adhesive tape at a quartz plate placed in a microwave resonance cavity and photoexcited at 355 nm. Figure a shows the pseudo-photoconductivity (ϕΣμ) transients of 1 , 2 , 5 , and 6 .…”

Hydrogen-bonded porous frameworks constructed by rigid π-conjugated molecules with carboxy groups

“…Moreover, solubility of the molecule in common organic solvents such as alcohol and N,N-dimethylformamide (DMF) can be improved when a carboxyphenyl group is applied instead of a carboxy group [86,87]. The phenylene spacer is also effective to generate void spaces in crystals [88][89][90].…”