RESUMEN
Conjugated π-surfaces are ubiquitous in molecules and materials. However, large π-surfaces up to a few nanometers in size are difficult to construct in an atomically precise manner. They tend to aggregate because of strong π-π interactions, resulting in notorious problems for both purification and spectroscopic investigations. Here, by contrast, we report the design, synthesis, and full characterizations of a nonplanar nanographene 1, which has a large, precise, and nonstacked π-surface. It is soluble in common organic solvents and allows for thorough investigations. The structure of 1, comprising 85 fused rings with an extended π-surface of 3 nm in size, is unambiguously confirmed by single-crystal X-ray diffraction. Unusual electronic structures, record-high near-infrared absorption, pronounced magnetic shielding, and ultrastrong heteromolecular van der Waals complexations are demonstrated, enabling us to establish a clear structure-property relationship, which has been elusive for decades. These results have broad implications for studying and understanding various phenomena and processes relevant to both discrete and interacting π-surfaces.
RESUMEN
This work describes a synthetic chiral graphene nanoribbon, named supertwistacene 1. It has four superbenzene (HBC) units linearly fused in a helical manner. The structure of 1, 4.3 nm in length, with an end-to-end twist of 117°, was confirmed by single-crystal X-ray diffraction. In contrast to various twistacene compounds and their analogues, 1 has a very stable configuration. It resists thermal isomerization even when being heated at 200 °C for 16 h. Enantiopure 1 obtained by chiral HPLC shows distinct CD signals in a broad spectral range until 600 nm. In addition, two smaller congeners of 1, the trimer 2 and the dimer 3, were also prepared and systematically investigated. Combining theoretical and experimental studies on 1-3 presents a big picture on their (chir)optical and electronic characteristics.
RESUMEN
Herein we present the first hexapole [9]helicene (H9H). Co-catalyzed [2+2+2] cyclotrimerization of a dinaphthopyrene (DNP) functionalized alkyne provides the hexaaryl benzene precursor 2, which is transformed into H9H via a dehydrocyclization reaction. Formation of each embedded [9]helicene involves forging of a new C-C bond, which stitches together two [4]helicene subunits of the neighboring DNP blades, reminiscent of the initial method Martin developed for the preparation of [9]helicene in the 1960s. Single-crystal X-ray analysis of both 2 and H9H discloses their extremely distorted and crowded structural features. Chiral resolution, optical and electronic properties of H9H are also presented.
