Chemistry Reference
In-Depth Information
Br
O
O
(HO)
2
B
KN(SiMe
3
)
2
98%
Pd(OAc)
2
,P
t
Bu
3
Cs
2
CO
3
93%
125
141
140
142a
142b
143
Scheme 44 Synthesis of naphthosumanene derivatives [
156
]
bowl depth of heteroatom-substituted analogues 132 and 133 were determined to be
0.79 and 0.23
, respectively. The longer C-X bond length mainly causes their
flattened structures. In contrast, triazasumanene 139 has a deeper bowl depth
(1.30
Å
) and a more curved structure. POAV pyramidalization angles of the hub
carbons were determined as 9.8
and 10.8
[
153
].
The symmetry aligned columnar order of sumanene (2) in the solid state [
136
]
allows it to have potential applications as an organic material. By using time-
resolved microwave conductivity (TRMC) method, the charge carrier mobility of
the needle-like single crystal of 2 demonstrated the large intracolumnar electron
mobility (0.75 cm
2
V
1
Å
s
1
) and its remarkable anisotropy along the
-bowl
π
stacking column axis [
154
].
Sumanene (2) and sumanenetrione (120) have similar bowl structures, but
different electronic properties [
155
]. Their nanocrystals can form core-shell assem-
blies, and aggregates of 120 are wrapped by nanocrystals of 2. The assemblies
showed that amplified photoluminescence of sumanenetrione nanocrystals was
caused by energy transfer from sumanene nanocrystals through the nanocrystalline
interface.
3.2 Naphthosumanenes
The methylene bridge of sumanene can be used for C-C bond formation for
expanding the backbone of the
-bowl. The synthesis started with bromosumanene
125, which was generated by selective monobromination of 2 with HBr
3
pyridine
complex (Scheme
44
)[
156
]. The Suzuki coupling of 125 with 2-formylphenylboronic
π
