16 research outputs found
Dithieno-Fused Polycyclic Aromatic Hydrocarbon with a Pyracylene Moiety: Strong Antiaromatic Contribution to the Electronic Structure
A synthetic route
to dithieno-fused CP-PAHs with a pyracylene segment
is reported. A combination of experimental and theoretical studies
revealed a strong contribution of antiaromatic character to the electronic
structure of this dithieno-fused CP-PAH. Anisotropy of current-induced
density (ACID) calculations indicated a significantly increased paramagnetic
ring current on the two pentagonal rings, which is more prominent
than that of the dibenzo-fused analogue. Furthermore, enhanced electron
affinity and a consequently decreased HOMO–LUMO gap were observed
for this dithieno-fused CP-PAH
Dithieno-Fused Polycyclic Aromatic Hydrocarbon with a Pyracylene Moiety: Strong Antiaromatic Contribution to the Electronic Structure
A synthetic route
to dithieno-fused CP-PAHs with a pyracylene segment
is reported. A combination of experimental and theoretical studies
revealed a strong contribution of antiaromatic character to the electronic
structure of this dithieno-fused CP-PAH. Anisotropy of current-induced
density (ACID) calculations indicated a significantly increased paramagnetic
ring current on the two pentagonal rings, which is more prominent
than that of the dibenzo-fused analogue. Furthermore, enhanced electron
affinity and a consequently decreased HOMO–LUMO gap were observed
for this dithieno-fused CP-PAH
Dithieno-Fused Polycyclic Aromatic Hydrocarbon with a Pyracylene Moiety: Strong Antiaromatic Contribution to the Electronic Structure
A synthetic route
to dithieno-fused CP-PAHs with a pyracylene segment
is reported. A combination of experimental and theoretical studies
revealed a strong contribution of antiaromatic character to the electronic
structure of this dithieno-fused CP-PAH. Anisotropy of current-induced
density (ACID) calculations indicated a significantly increased paramagnetic
ring current on the two pentagonal rings, which is more prominent
than that of the dibenzo-fused analogue. Furthermore, enhanced electron
affinity and a consequently decreased HOMO–LUMO gap were observed
for this dithieno-fused CP-PAH
Synthesis of Open-Cage Ketolactam Derivatives of Fullerene C<sub>60</sub> Encapsulating a Hydrogen Molecule
A novel open-cage fullerene C<sub>60</sub> derivative having a
bisÂ(hemiketal) moiety was synthesized by the reaction of C<sub>60</sub>-<i>N</i>-MEM-ketolactam (MEM: 2-methoxyethoxymethyl) with <i>N</i>-methylmorpholine <i>N</i>-oxide in the presence
of water. The structure was clearly determined by single crystal X-ray
analysis. Further enlargement of the opening was performed by treatment
with trifluoroacetic anhydride to give the tetraketo derivative having
a 15-membered ring opening. For H<sub>2</sub>-insertion into the cage,
the derivative was exposed to a high pressure of H<sub>2</sub>. After
the encapsulation, the opening size was reduced to the original one
while keeping the hydrogen molecule inside the cage. This compound
can be a possible precursor for endohedral azafullerenes encapsulating
a hydrogen molecule
Co(I)-Mediated Removal of Addends on the C<sub>60</sub> Cage and Formation of the Monovalent Cobalt Complex CpCo(CO)(η<sup>2</sup>‑C<sub>60</sub>)
The
removal of addends on the fullerene C<sub>60</sub> cage plays
an important role in the final stage for synthesizing endohedral fullerenes
by the molecular surgery method. We developed a cobalt-mediated reaction
to regenerate C<sub>60</sub> from <i>N</i>-substituted C<sub>60</sub> derivatives (aziridinofullerene and azafulleroid). In these
reactions, we found the formation of a green monovalent-cobalt complex
of C<sub>60</sub>, and its structure was unambiguously determined
by X-ray analysis. The characteristic electronic structure of this
cobalt complex was studied by IR and UV–vis absorption spectroscopy
and electrochemical analyses
Synthesis and Properties of Endohedral Aza[60]fullerenes: H<sub>2</sub>O@C<sub>59</sub>N and H<sub>2</sub>@C<sub>59</sub>N as Their Dimers and Monomers
The
macroscopic-scale syntheses of the first endohedral aza[60]Âfullerenes
X@C<sub>59</sub>N (X = H<sub>2</sub>O, H<sub>2</sub>) were achieved
in two different ways: (1) synthesis from endohedral fullerene H<sub>2</sub>O@C<sub>60</sub> as a starting material and (2) molecular
surgical synthesis from a C<sub>59</sub>N precursor having a considerably
small opening. In the neutral state of H<sub>2</sub>O@C<sub>59</sub>N, we expected the H-bonding interaction or repulsive N–O
interaction between entrapped H<sub>2</sub>O and a nitrogen atom on
the C<sub>59</sub>N cage. However, an attractive electrostatic N–O
interaction was suggested from the results of variable temperature
NMR, nuclear magnetic relaxation times (<i>T</i><sub>1</sub>, <i>T</i><sub>2</sub>), and density functional theory
(DFT) calculations. Upon the reaction with acetone via cationic intermediate
C<sub>59</sub>N<sup>+</sup>, we found a difference in reaction rates
between H<sub>2</sub>O@C<sub>59</sub>N and H<sub>2</sub>@C<sub>59</sub>N dimers (observed reaction rates: <i>k</i>′(H<sub>2</sub>O)/<i>k</i>′(H<sub>2</sub>) = 1.74 ±
0.16). The DFT calculations showed thermal stabilization of C<sub>59</sub>N<sup>+</sup> by entrapped H<sub>2</sub>O through the electrostatic
interaction
Palladium-Catalyzed Cyclization: Regioselectivity and Structure of Arene-Fused C<sub>60</sub> Derivatives
The
palladium-catalyzed cyclization on the fullerene C<sub>60</sub> cage
has been achieved using several aryl halides and C<sub>60</sub>. This
reaction was found to be accelerated by the addition of pivalic
acid, which can be rationally explained by the computational study
based on the concerted metalation–deprotonation mechanism.
We also demonstrated the regioselective π-functionalization
using prefunctionalized designed molecules possessing the same substructure
on the C<sub>60</sub> cage. The single crystal X-ray analysis and
electrostatic potential map revealed that the orientation of entrapped
H<sub>2</sub>O inside the naphthalene-fused open-cage C<sub>60</sub> derivative is electrostatically demanded due to the naphthalene-fusion
and construction of the opening
Orientation of a Water Molecule: Effects on Electronic Nature of the C<sub>59</sub>N Cage
A hydrogen-bonding
network is a key impelling force for an assembly
in bulk water. The fullerene cage can incarcerate a water molecule
without hydrogen-bonding. Herein, we focused on spin system H<sub>2</sub>O@C<sub>59</sub>N<sup>·</sup>. The <sup>1</sup>H NMR
relaxation time of entrapped H<sub>2</sub>O was significantly reduced
by the paramagnetic effect. Interestingly, the electron affinity and
ionization energy were suggested to vary depending on the orientation
of entrapped H<sub>2</sub>O owing to the degree of the partial charge
transfer from entrapped H<sub>2</sub>O to C<sub>59</sub>N<sup>·</sup>
Co(I)-Mediated Removal of Addends on the C<sub>60</sub> Cage and Formation of the Monovalent Cobalt Complex CpCo(CO)(η<sup>2</sup>‑C<sub>60</sub>)
The
removal of addends on the fullerene C<sub>60</sub> cage plays
an important role in the final stage for synthesizing endohedral fullerenes
by the molecular surgery method. We developed a cobalt-mediated reaction
to regenerate C<sub>60</sub> from <i>N</i>-substituted C<sub>60</sub> derivatives (aziridinofullerene and azafulleroid). In these
reactions, we found the formation of a green monovalent-cobalt complex
of C<sub>60</sub>, and its structure was unambiguously determined
by X-ray analysis. The characteristic electronic structure of this
cobalt complex was studied by IR and UV–vis absorption spectroscopy
and electrochemical analyses
Synthesis and Structure of an Open-Cage Thiafullerene C<sub>69</sub>S: Reactivity Differences of an Open-Cage C<sub>70</sub> Tetraketone Relative to Its C<sub>60</sub> Analogue
An
open-cage C<sub>70</sub> fullerene with a 13-membered ring-opening
and a bisÂ(hemiacetal) moiety was synthesized by the reaction of the
corresponding open-cage C<sub>70</sub> diketone with nucleophilic
oxidizing agents. The size of the cage opening could be expanded by
a subsequent dehydration reaction. Reaction of the thus obtained open-cage
C<sub>70</sub> tetraketone with elemental sulfur in the presence of
tetrakisÂ(dimethylamino)Âethylene resulted in the formation of the first
example of an open-cage C<sub>69</sub>S thiafullerene with a 12-membered
ring-opening. The formation of this sulfur-containing heterofullerene
reflects a significantly different chemical reactivity for the open-cage
C<sub>70</sub> tetraketone relative to its C<sub>60</sub> analogue.
The structures of all novel compounds were unambiguously determined
by single crystal X-ray diffraction analyses, in addition to which
the electrochemical properties of the thiafullerene C<sub>69</sub>S were examined and compared with those of the corresponding C<sub>70</sub> analogue