The syntheses of the 2,9‐dimesityl‐1,10‐phenanthroline (
Nanographene-Fused Expanded Carbaporphyrin Tweezers
A nanographene-fused expanded carbaporphyrin (5) and its BF2 complex (6)
were synthesized. Single-crystal X-ray structures revealed that 5 and 6 are connected by two
hexa-peri-hexabenzocoronene (HBC) units and two dipyrromethene or BODIPY units,
respectively. As prepared, 5 and 6 both show nonaromatic character with figure-of-eight
carbaoctaphyrin (1.1.1.0.1.1.1.0) cores and adopt tweezers-like conformations characterized
by a partially confined space between the two constituent HBC units. The distance between
the HBC centers is >10 Å, while the dihedral angles between the two HBC planes are 30.5
and 35.2° for 5 and 6, respectively. The interactions between 5 and 6 and fullerene C60 were
studied both in organic media and in the solid state. Proton NMR spectral titrations of 5 and
6 with C60 revealed a 1:1 binding mode for both macrocycles. In toluene-d8, the
corresponding binding constants were determined to be 1141 ± 17 and 994 ± 10 M−1 for 5
and 6, respectively. Single-crystal X-ray diffraction structural analyses confirmed the
formation of 1:1 fullerene inclusion complexes in the solid state. The C60 guests in both
complexes are found within triangular pockets composed of two HBC units from the tweezers-like receptor most closely associated
with the bound fullerene, as well as an HBC unit from an adjacent host. Femtosecond transient absorption measurements revealed
subpicosecond ultrafast charge separation between 5 (and 6) and C60 in the complexes. To the best of our knowledge, the present
report provides the first example wherein a nanographene building block is incorporated into the core of a porphyrinic framework.
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- Award ID(s):
- 2304731
- PAR ID:
- 10532450
- Editor(s):
- Carreira, Erick M
- Publisher / Repository:
- ACS Publications
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 146
- Issue:
- 1
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 543 to 551
- Subject(s) / Keyword(s):
- carboporhyrin expanded carboporphyrin tweezers
- Format(s):
- Medium: X Other: pdf
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/jacs.3c10122
