Three-Dimensional Aromatic Networks

Abstract

Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.

Oxidation State-Dependent Intramolecular Electronic Interaction of Carbazole-Based Azacyclophanes with 9,10-Anthrylene Units

“…Several Cz oligomers have found applications as functional materials in a variety of devices such as organic field-effect transistors, organic light-emitting diodes, and organic photovoltaics . 3,6-Substituted Cz derivatives and oligo­(3,6-Cz) have been extensively studied because of the ease of electrophilic aromatic substitutions at the 3,6-positions. , Recently, macrocycles have attracted intense interest due to their fascinating properties such as inclusion phenomena and supramolecular architectures . To design macrocyclic π-functional materials, the choice of spacers is important to realize the desired photochemical and electrochemical properties.…”

Synthesis and Electronic Properties of Length-Defined 9,10-Anthrylene–Butadiynylene Oligomers

“…Arylene oligomers composed of ethynylene or butadiynylene linkers offer versatile molecular designs for the construction of novel π-conjugated compounds . The structures and properties of such compounds are modified by varying the kind and number of arene units, the substitution position, and the kinds of linkers . Fundamental oligomers consisting of phenylene units have been extensively studied from various aspects, and their shapes are strongly dependent on the substitution positions .…”