Organic Letters
Letter
The electron-donor abilities of these PTAs were assessed by
ferrocene/ferrocium (Fc/Fc+) couple was used as a standard
(the HOMO energy level was taken to be −4.8 eV). The CV of
the ring-opened precursors (4, 6A, 6B) show irreversible
oxidation, while those of the ring-fused PTAs (5, 7, DPTA)
show reversible oxidation. The first oxidation peak Eox of 4 was
measured to be 1.31 eV and that of ferrocene is 0.55 eV; thus, the
HOMO of 4 is − [4.8 + (1.31 − 0.55)] = −5.56 eV. In the same
way, the HOMO of 5 and DPTA are −5.15 and −4.97 eV,
respectively. These results demonstrate that with the increase in
π-conjugation (from 4 to 5 and to DPTA) the HOMO energy
level becomes higher, and the electron-donating ability can be
ranked as 4 < 5 < DPTA. We noted that DPTA exhibits two
redox couples, which corresponds to two steps of charge transfer
and implies that the electronic donating may likely happen at the
bridge S atom.
In conclusion, we have developed a simple and efficient five-
step route to synthesize a series of π-extend sulfur-bridged pyrene
derivatives, finally leading to sulfur-containing DPTA with high
HOMO level and narrow energy gap. Two atropisomeric
precursors 6A and 6B have quite different properties, such as
chromatographic behaviors, packing styles, and solid-state
emissions. These compounds may be used as potential organic-
electronic materials.
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ASSOCIATED CONTENT
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13 (17), 4506−4509.
S
* Supporting Information
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Synthesis procedure, characterization, NMR, HRMS, CV,
X-ray structure, and DFT of PTAs (PDF)
Crystallographic data of 4 (CIF)
Crystallographic data of 5 (CIF)
Crystallographic data of 6A (CIF)
Crystallographic data of 6B (CIF)
Crystallographic data of 7 (CIF)
Crystallographic data of m-DPTA (CIF)
Crystallographic data of t-DPTA (CIF)
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AUTHOR INFORMATION
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Corresponding Authors
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by the National Natural Science
Foundation of China (Grant Nos. 21472116, 20972089, and
21672130) and the State Key Laboratory of Crystal Materials.
DEDICATION
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Dedicated to Prof. Thomas C. W. Mak on the occasion of his
80th birthday.
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Org. Lett. XXXX, XXX, XXX−XXX