11 research outputs found
Inter- and Intramolecular Electron-Transfer Reduction Properties of Coronenediimide Derivatives via Photoinduced Processes
Coronenediimide
derivatives with five- or six-membered maleimide groups [denoted as
Cor(5Im)<sub>2</sub> and Cor(6Im)<sub>2</sub>] were employed as electron
acceptors to examine the electron-transfer reduction properties through
photochemical and electrochemical measurements. In steady-state absorption
and fluorescence measurements, the spectra of Cor(5Im)<sub>2</sub> and Cor(6Im)<sub>2</sub> became remarkably broadened and red-shifted
as compared to pristine coronene (Cor). These results are supported
by electrochemical measurements and DFT calculations. The rate constants
of photoinduced intermolecular electron transfer from various donor
molecules to <sup>3</sup>Cor(5Im)<sub>2</sub>* or <sup>3</sup>Cor(6Im)<sub>2</sub>* are determined by nanosecond transient absorption measurements.
Although the back-electron-transfer reactions examined in this study
proceed with the diffusion-limited rate constant in benzonitrile (PhCN),
the rate constants of forward electron-transfer reactions (<i>k</i><sub>et</sub>) increase with an increase in the driving
force of electron transfer (−Δ<i>G</i><sub>et</sub>) to approach the diffusion-limited rate constant. When the
driving force dependence of <i>k</i><sub>et</sub> was fit
on the basis of the Marcus theory of electron transfer, the reorganization
energy (λ) of the electron-transfer reduction of Cor(5Im)<sub>2</sub> and Cor(6Im)<sub>2</sub> are determined to be 0.77 and 1.15
eV, respectively. A new covalently perylene-linked donor–acceptor
dyad was also synthesized to investigate the dynamics of ultrafast
photoinduced intramolecular electron transfer
Synthesis, Structural and Photophysical Properties of Pentacene Alkanethiolate Monolayer-Protected Gold Nanoclusters and Nanorods: Supramolecular Intercalation and Photoinduced Electron Transfer with C<sub>60</sub>
6,13-Bis(triisopropylsilylethynyl)-pentacene
(TIPS-pentacene: TP)
alkanethiolate monolayer-protected gold nanoclusters (TP-C<i>n</i>-<i>X</i>-MPCs: <i>X</i> stands for
small (<i>S</i>) and large (<i>L</i>) nanocluter
sizes) and nanorods (TP-C<i>n</i>-MPRs) with different alkyl
chain lengths (<i>n</i> = 7, 11) were synthesized to examine
the structural and photophysical properties as well as intercalation
trends with C<sub>60</sub>. The syntheses of TP-C<i>n</i>-<i>X</i>-MPCs and TP-C<i>n</i>-MPRs were successfully
performed using two different precursors: TP disulfides and TP alkanethiols.
The detailed structural properties were confirmed by <sup>1</sup>H
NMR, elemental analyses, and transmission electron micrograph (TEM).
In the spectroscopic absorption and fluorescence excitation measurements,
spectral shapes of TP units on the gold surface were clearly observed,
whereas fluorescence intensities of TP units were strongly quenched
as compared to the corresponding reference monomer (TP-Ref). Then,
fluorescence quenching titration experiments to determine the association
constants (<i>K</i><sub>app</sub>) between C<sub>60</sub> and TP assemblies (TP-C<i>n</i>-<i>X</i>-MPCs
and TP-C<i>n</i>-MPRs) were performed by adding C<sub>60</sub> in toluene. The <i>K</i><sub>app</sub> values were largely
dependent on the sizes of nanoclusters and alkyl chain lengths in
TP-C<i>n</i>-<i>X</i>-MPC. For example, the <i>K</i><sub>app</sub> value of TP-C7-<i>S</i>-MPC (73 800
M<sup>–1</sup>) was much larger than those of TP-C11-<i>S</i>-MPC (37 800 M<sup>–1</sup>) and TP-C7-<i>L</i>-MPC (5350 M<sup>–1</sup>). This trend is in sharp
contrast with the similar <i>K</i><sub>app</sub> values
(∼66 000 M<sup>–1</sup>) in TP-C<i>n</i>-MPR (<i>n</i> = 7, 11). These results suggest that the
intercalation behaviors are dependent on the surface structures (nanocluster
vs nanorod). Such fluorescence quenching processes by photoinduced
electron transfer (PET) in the complex between TP-C7-<i>S</i>-MPC and C<sub>60</sub> were directly observed by femtosecond transient
absorption measurements, monitoring the TP radical cation and C<sub>60</sub> radical anion
Broadband Light Harvesting and Fast Charge Separation in Ordered Self-Assemblies of Electron Donor–Acceptor-Functionalized Graphene Oxide Layers for Effective Solar Energy Conversion
Three-dimensionally (3D) ordered
assemblies of GO layers functionalized
with tetrakis(1-methylpyridinium-4-yl)porphyrin <i>p</i>-toluenesulfonate (Por), <i>N</i>,<i>N</i>′-di(2-(trimethylammonium
iodide)ethylene) perylenediimide (PDI), and Zn(II) phthalocyanine
tetrasulfonic acid (ZnPc) were obtained in water. Proper molar ratio
is essential between the cationic dyes, Por and PDI, acting as the
“glue” molecules to combine the GO layers and the anionic
ZnPc, acting as dispersant of GO layers to (i) construct the 3D assemblies
and (ii) the proportional absorption distribution of dye-functionalized
GO assemblies. Resulting 3D structures effectively harvest the light
from ultraviolet to near-infrared (NIR) regions. Dye molecules are
arranged in mainly lateral order on the GO layers with partial stacking,
which allows direct interactions with the π-conjugations of
the GO surface in 3D architecture. Ultrafast charge separation upon
the photoexcitation of the dyes at various wavelengths in the visible/NIR
region was observed in these assemblies, in which ZnPc and PDI were
the ultimate electron donor and acceptor, respectively. Lateral charge
migration among the partially stacked dye molecules was inferred from
the decay characteristics of the radical ion pair. Triggered by the
charge separation processes in the 3D ordered self-assemblies, significantly
higher photocurrent density in the OTE/SnO<sub>2</sub> electrode deposited
with self-assemblies of (GO–Por–PDI–ZnPc)<sub><i>n</i></sub> was generated compared to those deposited
with only GO or dye components
Multiexciton Dynamics Depending on Intramolecular Orientations in Pentacene Dimers: Recombination and Dissociation of Correlated Triplet Pairs
Pentacene
dimers bridged by a phenylene at ortho and meta positions
[denoted as <i>o</i>-(Pc)<sub>2</sub> and <i>m</i>-(Pc)<sub>2</sub>] were synthesized to examine intramolecular orientation-dependent
multiexciton dynamics, especially focusing on singlet fission (SF)
and recombination from correlated triplet pairs [(TT)]. Absorption
and electrochemical measurements indicated strong intramolecular couplings
of <i>o</i>-(Pc)<sub>2</sub> relative to <i>m</i>-(Pc)<sub>2</sub>. Femtosecond and nanosecond TA measurements successfully
demonstrated efficient SF in both dimers. In contrast, the dissociation
process from the (TT) to the individual triplets [(2 × T)] was
clearly observed in <i>m</i>-(Pc)<sub>2</sub>, which is
in sharp contrast to a major recombination process in <i>o</i>-(Pc)<sub>2</sub>. Time-resolved electron spin resonance (TR-ESR)
measurements demonstrated that the recombination and dissociation
proceed from the quintet state of <sup>5</sup>(TT) in <i>m</i>-(Pc)<sub>2</sub>. The rate constant of the SF was 2 orders of magnitude
greater in <i>o</i>-(Pc)<sub>2</sub> than that in <i>m</i>-(Pc)<sub>2</sub> and was rationalized by enhanced electronic
coupling between adjacent HOMOs of the Pc units
Zinc Phthalocyanine–Graphene Hybrid Material for Energy Conversion: Synthesis, Characterization, Photophysics, and Photoelectrochemical Cell Preparation
Graphene exfoliation upon tip sonication in <i>o</i>-dichlorobenzene
(<i>o</i>-DCB) was accomplished. Covalent grafting of (2-aminoethoxy)(tri-<i>tert</i>-butyl) zinc phthalocyanine (ZnPc) to exfoliated graphene
sheets was then achieved. The newly formed ZnPc–graphene hybrid
material was found to be soluble in common organic solvents without
any precipitation for several weeks. Application of diverse spectroscopic
techniques verified the successful formation of the ZnPc–graphene
hybrid material, while thermogravimetric analysis revealed the amount
of ZnPc loading onto graphene. Microscopy analysis based on AFM and
TEM was applied to probe the morphological characteristics and to
investigate the exfoliation of graphene sheets. Efficient fluorescence
quenching of ZnPc in the ZnPc–graphene hybrid material suggested
that photoinduced events occur from the photoexcited ZnPc to exfoliated
graphene. The dynamics of the photoinduced electron transfer was evaluated
by femtosecond transient absorption spectroscopy, thus revealing the
formation of transient species such as ZnPc<sup>•+</sup>, yielding
the charge-separated state ZnPc<sup>•+</sup>–graphene<sup>•–</sup>. Finally, the ZnPc–graphene hybrid
material was integrated into a photoactive electrode of an optical
transparent electrode (OTE) cast with nanostructured SnO<sub>2</sub> films (OTE/SnO<sub>2</sub>), which exhibited stable and reproducible
photocurrent responses, and the incident photon-to-current conversion
efficiency was determined
Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission
Intramolecular
singlet fission (ISF) is a promising photophysical
process to construct more efficient light energy conversion systems
as one excited singlet state converts into two excited triplet states.
Herein we synthesized and evaluated bent-shaped pentacene dimers as
a prototype of ISF to reveal intrinsic characters of triplet states
(e.g., lifetimes of triplet excited states). In this study, <i>meta-</i>phenylene-bridged TIPS-pentacene dimer (PcD-3Ph) and
2,2′-bipheynyl bridged TIPS-pentacene dimer (PcD-Biph) were
newly synthesized as bent-shaped dimers. In the steady-state spectroscopy,
absorption and emission bands of these dimers were fully characterized,
suggesting the appropriate degree of electronic coupling between pentacene
moieties in these dimers. In addition, the electrochemical measurements
were also performed to check the electronic interaction between two
pentacene moieties. Whereas the successive two oxidation peaks owing
to the delocalization were observed in a directly linked-pentacene
dimer (PcD) by a single bond, the cyclic voltammograms in PcD-Biph
and PcD-3Ph implied the weaker interaction compared to that of <i>p-</i>phenylene-bridged TIPS-pentacene dimer (PcD-4Ph) and PcD.
The femtosecond and nanosecond transient absorption spectra clearly
revealed the slower ISF process in bent-shaped pentacene dimers (PcD-Biph
and PcD-3Ph), more notably, the slower relaxation of the excited triplet
states in PcD-Biph and PcD-3Ph. Namely, the quantum yields of triplet
states (Φ<sub>T</sub>) by ISF approximately remain constant
(ca. 180–200%) in all dimer systems, whereas the lifetimes
of the triplet excited states became much longer (up to 360 ns) in
PcD-Biph as compared to PcD-4Ph (15 ns). Additionally, the lifetimes
of the corresponding triplet states in PcD-Biph and PcD-3Ph were sufficiently
affected by solvent viscosity. In particular, the lifetimes of PcD-Biph
triplet state in THF/paraffin (1.0 μs) increased up to approximately
three times as compared to that in THF (360 ns), whereas those of
PcD-4Ph were quite similar in both solvent
Siloxy Group-Induced Highly Efficient Room Temperature Phosphorescence with Long Lifetime
The
design and development of organic phosphors that exhibit efficient
emission at room temperature but do not contain precious metals such
as iridium and platinum have attracted increasing attention. We report
herein highly efficient green phosphorescence-emitting 1,4-dibenzoyl-2,5-bis(siloxy)benzene
crystals in air at room temperature. Remarkable luminescence quantum
yields of 0.46 to 0.64 and long lifetimes ranging from 76.0 to 98.3
ms were observed. X-ray diffraction analysis of the single crystals
revealed that there were several intermolecular interactions causing
suppression of intramolecular motion, thereby minimizing nonradiative
decay of the triplet excited state. Comparison with the corresponding
2,5-bis(dimethylphenylsilylmethyl) and 2,5-bis(trimethylsilyl) derivatives
revealed that the siloxy groups are essential for efficient room temperature
phosphorescence. Density functional calculations suggested that σ–n
conjugation was operative in the siloxy moieties. Electron spin resonance
measurement indicated that the radiative process included generation
of the triplet diradical species, whose electron distribution was
very similar to that of naphthalene. The present study largely expands
the possibilities for the molecular design of precious metal- and
halogen-free organic phosphors exhibiting efficient room temperature
phosphorescence
Highly Fluorescent [7]Carbohelicene Fused by Asymmetric 1,2-Dialkyl-Substituted Quinoxaline for Circularly Polarized Luminescence and Electroluminescence
A new
1,2-dialkylquinoxaline-fused [7]carbohelicene ([7]Hl-NAIQx)
was designed and synthesized by asymmetrically introducing two alkyl
chains onto the quinoxaline unit. Direct alkylation of the quinoxaline
ring of quinoxaline-fused helicene leads to discontinuity in the conjugated
structure. In the single-crystal analysis, the parent quinoxaline-fused
[7]carbohelicene ([7]Hl-Qx) was found to have a helical structure
formed by two phenanthrene units and a nonplanar twisted angle between
the phenanthrene and quinoxaline units. In contrast, [7]Hl-NAIQx possesses
an almost planar aromatic structure between the alkyl-quinoxaline
and phenanthrene units (torsion angle: 179°), in addition to
the similar helical structure between the two phenanthrene units.
The steady-state absorption, fluorescence, and circular dichroism
(CD) spectra of [7]Hl-NAIQx were significantly red-shifted compared
to those of [7]Hl-Qx and [7]carbohelicene ([7]Hl). These spectral
changes were mainly explained by electrochemical measurements and
density functional theory calculations. Moreover, the absolute fluorescence
quantum yield (Φ<sub>FL</sub>) of [7]Hl-NAIQx was 0.25, which
is more than 10 times larger than that of the reference [7]Hl (Φ<sub>FL</sub> = 0.02). Such a large enhancement of the fluorescence of
[7]Hl-NAIQx has provided excellent circularly polarized luminescence
(CPL). The value of the anisotropy factor <i>g</i><sub>lum</sub> (normalized difference in emission of right-handed and left-handed
circularly polarized light) was estimated to be 4.0 × 10<sup>–3</sup>. The electroluminescence of an organic light-emitting
diode utilizing [7]Hl-NAIQx was successfully observed
Synthetic Control of Photophysical Process and Circularly Polarized Luminescence of [5]Carbohelicene Derivatives Substituted by Maleimide Units
A series
of [5]carbohelicene derivatives substituted by electron-withdrawing
maleimide and electron-donating methoxy, such as maleimide-substituted
[5]carbohelicene (HeliIm) and methoxy-substituted HeliIm (MeO-HeliIm),
were newly designed and synthesized to examine the electrochemical
properties, excited-state dynamic and circularly polarized luminescence
(CPL). First, electrochemical measurements and DFT calculations of
[5]carbohelicene derivatives were performed by comparing with the
structural isomers: picene derivatives. Introduction of an electron-withdrawing
maleimide group onto a [5]carbohelicene core contributes to the stabilized
LUMO state in HeliIm as compared to that of [5]carbohelicene (Heli),
whereas the energy level of HOMO state in MeO-HeliIm increases by
introducing electron-donating methoxy (MeO) groups onto a HeliIm skeleton.
The HOMO–LUMO gap of MeO-HeliIm is smaller than those of HeliIm
and Heli, which is similar to the steady-state spectroscopic measurements.
The absolute fluorescence quantum yield (Φ<sub>FL</sub>) of
HeliIm (0.37) largely increased as compared to [5]carbohelicene, Heli
(0.04), whereas Φ<sub>FL</sub> of MeO-HeliIm (0.22) was slightly
smaller than that of HeliIm. Theses photophysical processes including
intersystem crossing are successfully explained by the kinetic discussions.
Since [5]carbohelicene derivatives show the chirality, measurements
of circular dichroism (CD) and circularly polarized luminescence (CPL)
were successfully performed. In particular, HeliIm and MeO-HeliIm
have provide excellent circularly polarized luminescence (CPL) and
the values of the anisotropy factor <i>g</i><sub>lum</sub> were estimated to be ∼2.4 × 10<sup>–3</sup> and
∼2.3 × 10<sup>–3</sup>, relatively. This is the
first observation of CPL in [5]carbohelicene derivatives
Controlled Excited-State Dynamics and Enhanced Fluorescence Property of Tetrasulfone[9]helicene by a Simple Synthetic Process
Tetrasulfone[9]helicene (PTSH) was
newly synthesized to improve
and evaluate its fluorescence and excited-state dynamics through a
single-step oxidation reaction of tetrathia[9]helicene (PTTH). In
electrochemical measurements, the reduction potential of PTSH was
shifted in a positive direction by approximately 1.0 V when compared
to that of PTTH because of its electron-accepting sulfone units. The
results of the electrochemical measurements agree with the energy
levels calculated by density functional theory (DFT) methods and steady-state
spectroscopic measurements. Furthermore, a significant enhancement
of the absolute fluorescence quantum yield (Φ<sub>FL</sub>)
was achieved. The absolute fluorescence quantum yield of PTSH attained
0.27, which is approximately 10 times larger than that of PTTH (Φ<sub>FL</sub> = 0.03). Such an enhancement of Φ<sub>FL</sub> can
be successfully explained by the corresponding kinetic comparison.
The reason is mainly the increased energy gap Δ<i><i>E</i></i><sub>ST</sub> between the lowest singlet (S<sub>1</sub>) and triplet (T<sub>1</sub>) excited states. Finally, excellent
circularly polarized luminescence of PTSH was also observed. The value
of the anisotropy factor <i>g</i><sub>CPL</sub> was estimated
to be 8.3 × 10<sup>–4</sup> in PTSH