Functionalized aromatics aligned with the three Cartesian axes: Extension of centropolyindane chemistry

Abstract

The unique geometrical features and structural potential of the centropolyindanes, a complete family of novel, 3D polycyclic aromatic hydrocarbons, are discussed with respect to the inherent orthogonality of their arene units. Thus, the largest member of the family, centrohexaindane, a topologically nonplanar hydrocarbon, is presented as a "Cartesian hexabenzene", because each of its six benzene units is stretched into one of the six directions of the Cartesian space. This feature is discussed on the basis of the X-ray crystal structures of centrohexaindane and two lower members of the centropolyindane family, viz. the parent tribenzotriquinacenes. Recent progress in multiple functionalization and extension of the indane wings of selected centropolyindanes is reported, including several highly efficient sixand eight-fold C-C cross-coupling reactions. Some particular centropolyindane derivatives are presented, such as the first twelve-fold functionalized centrohexaindane and a tribenzotriquinacene bearing three mutually orthogonal phenanthroline groupings at its molecular periphery. Challenges to further extend the arene peripheries of the tribenzotriquinacenes and fenestrindanes to give, eventually, graphite cuttings bearing a central bowl-or saddle-shaped center are outlined, as is the hypothetical generation of a "giant" nanocube consisting of eight covalently bound tribenzotriquinacene units. Along these lines, our recent discovery of a related, solid-state supramolecular cube, containing eight molecules of a particular tribromotrinitrotribenzotriquinacene of the same absolute configuration, is presented for the first time.

Handling Electromagnetic Radiation beyond Terahertz using Chromophores to Transition from Visible Light to Petahertz Technology

“…Finally, a skew-type arrangement allows both transitions (Figure 8 right, bottom) where the relative intensities and positions depend on the exact geometry. An orthogonal arrangement extinguishes the exciton interactions; this could be demonstrated with a trichromophoric dye [29] where a Cartesian-named backbone [30] places the three chromophores orthogonally into the three room directions.…”

Diamond D5, a Novel Class of Carbon Allotropes

“…There is a chance to reach D 5 just from C 17 , a centrohexaquinane (Paquette and Vazeux 1981;Kuck 2006) which can dimerize (Diudea and Nagy 2011b;Eaton 1979) to 2 Â C 17 ¼ C 34 and this last condensing to 4 Â C 17 ¼ C 51 (Fig. 11.9, top row).…”

Tris(tetraceno)triquinacenes: Synthesis and Photophysical Properties of Threefold Linearly Extended Tribenzotriquinacenes

“…[13] In the present work, three acene units have been incorporated into the three-dimensional framework of tribenzotriquinacene (TBTQ, 1). [14][15][16] This polycyclic hydrocarbon belonging to the centropolyindane family [17] has a conformationally rigid and highly symmetrical (C 3v ) carbon framework consisting of three indane wings oriented orthogonally to each other (A, Figure 1). [17][18][19] Owing to this unique spatial arrangement and the bowl-shaped architecture of 1, we expected increased solubility of threefold aceno-annellated triquinacenes, such as B, which would contribute a new facet to the field.…”

“…[28] Threefold application of this strategy within the same TBTQ framework appears to be impeded by the poor solubility of such extended structures at low temperatures. [17,29] Therefore, we now pursued an alternative, high-temperature strategy involving a threefold Diels-Alder reaction of TBTQ-based ortho-quinodimethanes with suitable dienophiles. [30] Under such conditions, the solubility of even threefold-extended intermediates and products was expected to be sufficiently enhanced.…”