Arching a bay area of triphenyleno[1,12-bcd]thiophene with group 14 functionalities: Synthesis of the first triphenylene derivatives having thiophene and metallafluorene moieties

Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds: Synthetic Routes, Properties, and Applications

“…The principal difficulty in synthesizing 153.7 lies in the high internal strain of the bowl, which must be energetically compensated during the cyclization process. Strain-free sumanene derivatives containing combinations of S, SiMe 2 , SnMe 2 , and GeMe 2 units were prepared by Saito et al using stepwise lithiation and electrophilic bridging of triphenylene, but trithiasumanene was not accessible using such an approach. − A successful route to substituted trithia- and triselenasumanenes ( 154.4 and 154.6 , Scheme ) was developed in 2014 by Shao et al , These compounds were obtained from hexabutoxytriphenylene 154.1 , which was directly lithiated and reacted with elemental sulfur or selenium, to yield “expanded” sumanenes containing one or two dichalcogen bridges ( 154.2 and 154.5 ). The latter compounds were contracted to the desired sumanenes by means of a Cu-mediated chalcogen extrusion.…”

Marriage of heavy main group elements with π-conjugated materials for optoelectronic applications

“…The Saito group reported the synthesis of triphenylenes containing externally bridging S, Si and Sn heteroatoms (111-113; Scheme 9). 117 In each case the heteroatom was installed by initially lithiating acidic positions about the triphenylene scaffold with an n BuLi/TMEDA (TMEDA = tetramethylethylenediamine) combination, followed by addition of the element dihalides SCl 2 , Me 2 SiCl 2 and Me 2 SnCl 2 . The Si and Sn analogues (112 and 113) have nearly identical absorbance spectra, and accordingly, computations indicate no orbital participation from the Si or Sn atoms to the HOMO and LUMO states.…”

The Chemistry of Heterasumanenes

“…Lithiation of a bay region in 19 followed by treatment with dichlorodimethylsilane afforded silolotriphenylenothione 20 . The use of dichlorodimethylstannane instead of dichlorodimethylsilane produced stannole derivative 21 (Scheme ) . Thus, we succeeded in the introduction of different heteroatoms into the triphenylene skeleton.…”

“…Thus, we succeeded in the introduction of different heteroatoms into the triphenylene skeleton. Similarly, by the use of sulfur dichloride, triphenylenodithiophene 22 was obtained …”