Sumanene derivatives fused by quinones and acenes were synthesized through Friedel‐Crafts double acylation, followed by reductive aromatization. Single‐crystal X‐ray diffraction analysis on synthesized quinone and acene derivatives revealed the one‐dimensional (1D) columnar stackings predominated by the concave‐convex alignment from sumanene moiety. The thus‐prepared sumanene‐fused acenes exhibited higher solubility to organic solvent and significant stability against aerobic oxidation than the pristine acenes.
2,3,5,6,8,9-Hexakis(phenoxycarbonyl)sumanene, a hexasubstituted sumanene with CO2Ph groups at the peripheral aromatic carbons, was successfully prepared in good yield by Pd-catalyzed phenoxycarbonylation using a solvent of phenyl formate. Single-crystal X-ray structural analysis of this compound revealed the formation of a one-dimensional columnar structure, stacked in a staggered manner. The UV and emission spectra of this showed clear red-shifts compared with those of pristine sumanene, indicating the extension of the conjugation system.
Hexakis(bromomethyl)sumanene, a hexasubstituted sumanene with bromomethyl groups at the peripheral aromatic carbons, was successfully synthesized in 97% yield with a one-step reaction. Single-crystal X-ray structural analysis showed a formation of a dimer structure.The nucleophilic substitution afforded the introduction of several substituents. These UV-vis absorption and emission spectra showed clear redshift compared with pristine sumanene, indicating the extension of the conjugation system of hexa-substituted sumanenes.
In this study, we found that a pristine buckybowl, sumanene, can form solution-state supramolecular polymers. We also demonstrated that sumanene supramolecular polymers can be dynamically controlled by external stimuli, in...
We investigate the
potential of sumanene-fused acenes as a novel
class of highly efficient singlet fission (SF) candidates by density
functional theory (DFT) calculations and exciton dynamics simulations
using the quantum master equation. The DFT calculations have revealed
that fusion of sumanene to oligoacenes enables columnar π–π
stacking with large electronic couplings. Moreover, the stacked curved
π-structure is found to significantly stabilize the charge transfer
state. As a result, these unique properties of sumanene-fused acenes
are found to drastically accelerate the SF dynamics in the dimer models.
Especially in a sumanene-fused tetracene dimer, SF rate is predicted
to be 3.46 times as large as that in a pentacene dimer model constructed
from the crystal structure. The present results demonstrate that fusion
of a curved π-molecule to an SF molecule can be a novel effective
strategy for designing more efficient SF materials.
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