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From Armchair to Zigzag Peripheries in Nanographenes

2006; American Chemical Society; Volume: 128; Issue: 29 Linguagem: Inglês

10.1021/ja062026h

1943-2984

Marcel Kastler, Jochen Schmidt, Wojciech Pisula, Daniel Sebastiani, Kläus Müllen,

Organic Electronics and Photovoltaics

Synthetic concepts toward the synthesis of large, not-fully benzenoid polycyclic aromatic hydrocarbons (PAHs), decorated with phase-forming and solubilizing n-dodecyl chains, are presented based on the intramolecular cyclodehydrogenation reaction of suitable oligophenylene precursors. The formal addition of successive C2 units into the armchair bays of the parent hexa-peri-hexabenzocoronene extends the aromatic system and leads to PAHs with a partial zigzag periphery. This variation of the nature of the periphery, symmetry, size, and shape has a distinct impact upon the electronic properties and the organization into columnar superstructures. Both computational and experimental UV/vis spectra, which are in good agreement, emphasize the dependence of the characteristic bands α, p, and β upon the overall size and symmetry of the PAHs. While the number and the substitution patterns of attached n-dodecyl chains do not influence the electronic properties, the thermal behavior and supramolecular organization are strongly influenced, which has been elucidated with differential scanning calorimetry (DSC) and 2D wide-angle X-ray diffractometry (2D-WAXS) on mechanically aligned samples. This study provides valuable insight into the future design of semiconducting materials based on extended PAHs.