Non‐Pyrolytic, Large‐Scale Synthesis of Trichalcogenasumanene: A Two‐Step Approach

Abstract

Trichalcogenasumanenes were synthesized on a multigram scale through a two-step approach that takes advantage of non-pyrolytic cyclization and solventless ring contraction. Solid-state structure and photophysical investigations demonstrate that these compounds are promising candidates for electronic materials.

Isolation and structures of some selenium and tellurium derivatives of 1, 4, 5, 8, 9, 12-hexabromododecahydrotriphenylene as co-crystals of triphenylene

“…In the present study we report our attempts to insert heteroatoms like selenium and tellurium at the peripheral positions of the triphenylene rings using nucleophilic substitution reaction without any substitution on the triphenylene rings. During the course of the present study, Shao and co-workers 10 have reported the insertion of sulfur and selenium heteroatoms at the peripheral positions of the triphenylene rings (16)(17). In this case they succeeded in incorporating sulfur and selenium by electrophilic substitution reaction using n-BuLi as reagent followed by chalcogen (S, Se) insertion.…”

Chiral Buckybowl Molecules

“…The higher the bowl inversion energy is, the more stable the chiral conformer will be. Several heterobuckybowls have been reported in the literature, some of them chiral ( Figure 9) [12,[58][59][60][61][62][63][64][65][66]. …”

“…More recently, Saito and co-workers prepared a triphosphasumanene trisulfide 13 derivative with a large dipole moment (12.0 D) [67]. The bowl depth of syn-isomer 13 is 0.46 Å, which is identical to triselenasumane 18 (0.47 Å) [64] and shallower than sumanene [24], whereas the anti-isomer of triphosphasumanene trisulfide 13 exists in an almost plane structure [67].…”

“…Introduction of heteroatoms in the periphery of buckybowls usually resulted in a decrease of the bowl depth of heterobuckybowls, because the bond lengths of carbon-heteroatom increased with the atomic size ( Figure 9). The bowl depths of trithiasumane 16 (0.79 Å) and triselenasumane 18 (0.47 Å) [64] have a shallower bowl depth than that of normal sumanene 2 (1.11 Å) [24]. Trisilicasumanene 12 [59,63] and tritellurasumanene 19 have a plane structure, whereas triazasumanene 10 has a deeper bowl depth of 1.30 Å because the C-N bond length (1.47 Å) is shorter than the C-C bond length (1.54 Å) [12].…”

Trichalcogenasumanene ortho‐Quinones: Synthesis, Properties, and Transformation into Various Heteropolycycles

“…[11] Heterasumanenes can be created by replacing i) the benzyl carbon atoms with S, P, Si, Sn, and Ge; [12][13][14][15] and ii)the outer benzene rings with pyridine rings. [17] Compounds 1a-c are electron-rich owing to the presence of butoxy groups and chalcogen-containing rings,a nd 1a,b show ring strain because of the curved structure.T herefore, 1a-c have multiple chemically active sites:t he outer electron-rich C=C bonds,c halcogen atoms,a nd butoxy groups (shown as paths A, B, and Ci nS cheme 1). [17] Compounds 1a-c are electron-rich owing to the presence of butoxy groups and chalcogen-containing rings,a nd 1a,b show ring strain because of the curved structure.T herefore, 1a-c have multiple chemically active sites:t he outer electron-rich C=C bonds,c halcogen atoms,a nd butoxy groups (shown as paths A, B, and Ci nS cheme 1).…”