Nonplanar Nanographene with a Large Conjugated π-Surface

Abstract

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.