16 research outputs found
Photochemistry of self-assembled donor-acceptor architectures for photoactive supramolecular devices
Supramolecular donor-acceptor assemblies were prepared and studied with spectro-scopic methods. The two main objectives of this work were: (i) fundamental study of photoinduced energy and electron transfer processes in self-assembled supramolecular donor-acceptor complexes in solutions and (ii) self-assembly and photophysical characterization of donor-acceptor ïŹlms on titanium dioxide (TiO2) surface. The study of these systems aims to develop more complex architectures for artificial photosynthesis and understand factors that affect efficiency of the photoinduced energy and electron transfer processes in natural and artificial photosynthesis. This knowledge can be used for building photoactive molecular devices such as organic solar cells.
The singlet excited state energy transfer in dyads formed via axial metalâligand coordination of free-base porphyrin to metal (Mg, Ru) complexes of pthalocyanine was observed. The position of imidazole linker group on one of the meso-aryl groups of the free-base porphyrin was used to tune the rates of energy transfer. The two-point binding provides better control over complex geometry and it was implemented utilizing metal-ligand and crown-ether coordination in zinc chlorinâfullerene supramolecular dyads. This approach allowed to increase the binding efficiency and achieve a well-deïŹned mutual orientation between the moieties. The electron transfer rate was found to depend on the donor-acceptor distance as well as the mutual orientation of the entities and could be manipulated by changing positions of binding groups.
The donor-acceptor layers were assembled on TiO2 using two methods. First, a layer of covalently linked porphyrin-pthalocyanine dyads was formed on TiO2 via supramolecular approach. Then, a new method was developed to construct donor-acceptor two-layer films using separate porphyrin and fullerene molecules. In both cases, photo-excitation of donor molecules resulted in charge-separation (CS) inside the organic layer and sequential electron transfer towards the TiO2. Furthermore, the charge recombination (CR) process was found to be slower than for systems sensitized with single chromophores
A Record Chromophore Density in High-Entropy Liquids of Two Low-Melting Perylenes: A New Strategy for Liquid Chromophores
Weinheim Liquid chromophores constitute a rare but intriguing class of molecules that are in high demand for the design of luminescent inks, liquid semiconductors, and solar energy storage materials. The most common way to achieve liquid chromophores involves the introduction of long alkyl chains, which, however, significantly reduces the chromophore density. Here, strategy is presented that allows for the preparation of liquid chromophores with a minimal increase in molecular weight, using the important class of perylenes as an example. Two synergistic effects are harnessed: (1) the judicious positioning of short alkyl substituents, and (2) equimolar mixing, which in unison results in a liquid material. A series of 1-alkyl perylene derivatives is synthesized and it is found that short ethyl or butyl chains reduce the melting temperature from 278 \ub0C to as little as 70 \ub0C. Then, two low-melting derivatives are mixed, which results in materials that do not crystallize due to the increased configurational entropy of the system. As a result, liquid chromophores with the lowest reported molecular weight increase compared to the neat chromophore are obtained. The mixing strategy is readily applicable to other Ï-conjugated systems and, hence, promises to yield a wide range of low molecular weight liquid chromophores
Photochemistry of self-assembled donor-acceptor architectures for photoactive supramolecular devices
Supramolecular donor-acceptor assemblies were prepared and studied with spectro-scopic methods. The two main objectives of this work were: (i) fundamental study of photoinduced energy and electron transfer processes in self-assembled supramolecular donor-acceptor complexes in solutions and (ii) self-assembly and photophysical characterization of donor-acceptor ïŹlms on titanium dioxide (TiO2) surface. The study of these systems aims to develop more complex architectures for artificial photosynthesis and understand factors that affect efficiency of the photoinduced energy and electron transfer processes in natural and artificial photosynthesis. This knowledge can be used for building photoactive molecular devices such as organic solar cells.
The singlet excited state energy transfer in dyads formed via axial metalâligand coordination of free-base porphyrin to metal (Mg, Ru) complexes of pthalocyanine was observed. The position of imidazole linker group on one of the meso-aryl groups of the free-base porphyrin was used to tune the rates of energy transfer. The two-point binding provides better control over complex geometry and it was implemented utilizing metal-ligand and crown-ether coordination in zinc chlorinâfullerene supramolecular dyads. This approach allowed to increase the binding efficiency and achieve a well-deïŹned mutual orientation between the moieties. The electron transfer rate was found to depend on the donor-acceptor distance as well as the mutual orientation of the entities and could be manipulated by changing positions of binding groups.
The donor-acceptor layers were assembled on TiO2 using two methods. First, a layer of covalently linked porphyrin-pthalocyanine dyads was formed on TiO2 via supramolecular approach. Then, a new method was developed to construct donor-acceptor two-layer films using separate porphyrin and fullerene molecules. In both cases, photo-excitation of donor molecules resulted in charge-separation (CS) inside the organic layer and sequential electron transfer towards the TiO2. Furthermore, the charge recombination (CR) process was found to be slower than for systems sensitized with single chromophores
Specific Imaging of Intracellular Lipid Droplets Using a Benzothiadiazole Derivative with Solvatochromic Properties
Altered lipid metabolism and extensive lipid storage in cells have been associated with various medical disorders, including cancer. The development of fluorescent probes that specifically accumulate in lipid deposits is therefore of great interest in order to study pathological processes that are linked to dysregulated lipogenesis. In the present study, we present a small fluorescent benzothiadiazole dye that specifically stains lipid droplets in living and fixated cells. The photophysical characterization of the probe revealed strong solvatochromic behavior, large Stokes shifts, and high fluorescent quantum yields in hydrophobic solvents. In addition, the fluorophore exhibits a nontoxic profile and a high signal-to-noise ratio in cells (i.e., lipid droplets vs cytosol), which make it an excellent candidate for studying lipid biology using confocal fluorescent microscopy.Funding Agencies|Swedish Research Council [350-2012-239]; Swedish Foundation of Strategic Research [ICA14-0018]; Wenner-Gren Foundation</p
Specific Imaging of Intracellular Lipid Droplets Using a Benzothiadiazole Derivative with Solvatochromic Properties
Altered
lipid metabolism and extensive lipid storage in cells have
been associated with various medical disorders, including cancer.
The development of fluorescent probes that specifically accumulate
in lipid deposits is therefore of great interest in order to study
pathological processes that are linked to dysregulated lipogenesis.
In the present study, we present a small fluorescent benzothiadiazole
dye that specifically stains lipid droplets in living and fixated
cells. The photophysical characterization of the probe revealed strong
solvatochromic behavior, large Stokes shifts, and high fluorescent
quantum yields in hydrophobic solvents. In addition, the fluorophore
exhibits a nontoxic profile and a high signal-to-noise ratio in cells
(i.e., lipid droplets vs cytosol), which make it an excellent candidate
for studying lipid biology using confocal fluorescent microscopy
Long-Range Observation of Exciplex Formation and Decay Mediated by One-Dimensional Bridges
We report herein
unprecedented long-range observation of both formation
and decay of the exciplex state in donor (D)âbridge (B)âacceptor
(A) linked systems. Zinc porphyrins (ZnP) as a donor were tethered
to single-walled carbon nanotube (SWNT) as an acceptor through oligoÂ(<i>p</i>-phenylene)Âs (ZnPâph<sub><i>n</i></sub>âSWNT) or oligoÂ(<i>p</i>-xylene)Âs (ZnPâxy<sub><i>n</i>â1</sub>âph<sub>1</sub>âSWNT)
with systematically varied lengths (<i>n</i> = 1â5)
to address the issue. Exponential dependencies of rate constants for
the exciplex formation (<i>k</i><sub>FEX</sub>) and decay
(<i>k</i><sub>DEX</sub>) on the edge-to-edge separation
distance between ZnP and SWNT through the bridges were unambiguously
derived from time-resolved spectroscopies. Distance dependencies (i.e.,
attenuation factor, ÎČ) of <i>k</i><sub>FEX</sub> and <i>k</i><sub>DEX</sub> in ZnPâph<sub><i>n</i></sub>âSWNT were found to be considerably small (ÎČ = 0.10
for <i>k</i><sub>FEX</sub> and 0.12 Ă
<sup>â1</sup> for <i>k</i><sub>DEX</sub>) compared to those for charge
separation and recombination (0.2â0.8 Ă
<sup>â1</sup>) in DâBâA systems with the same oligoÂ(<i>p</i>-phenylene) bridges. The small ÎČ values may be associated with
the exciplex state with mixed characters of charge-transfer and excited
states. In parallel, the substantially nonconjugated bridge of oligoÂ(<i>p</i>-xylene)Âs exhibited larger attenuation values (ÎČ
= 0.12 for <i>k</i><sub>FEX</sub> and 0.14 Ă
<sup>â1</sup> for <i>k</i><sub>DEX</sub>). These results provide deep
insight into the unique photodynamics of electronically strongly coupled
DâBâA systems involving exciplex
Photophysical Study of a Self-Assembled DonorâAcceptor Two-Layer Film on TiO<sub>2</sub>
The self-assembled monolayer (SAM)
technique was employed to fabricate a two-layer donorâacceptor
film on the surface of TiO<sub>2</sub>. The approach is based on using
donor and acceptor compounds with anchoring groups of different lengths.
The acceptor, a fullerene derivative, has a carboxyl anchor attached
to the fullerene moiety via a short linker that places the fullerene
close to the surface. The donor, a porphyrin derivative, is equipped
with a long linker that can penetrate between the fullerenes and keep
porphyrin on top of the fullerene layer. The two-layer fullereneâporphyrin
structures were deposited on a mesoporous film of TiO<sub>2</sub> nanoparticles
by immersing the TiO<sub>2</sub> film sequentially into fullerene
and porphyrin solutions. Transient absorption spectroscopy studies
of the samples revealed that after the selective photoexcitation of
porphyrin a fast (<5 ps) intermolecular electron transfer (ET)
takes place from porphyrin to the fullerene layer, which confirms
the formation of the interlayer donorâacceptor interface. Furthermore,
in the second step of ET the fullerene anions donate electrons to
the TiO<sub>2</sub> nanoparticles. The latter reaction is relatively
slow with an average time constant of 230 ps. It involves roughly
half of the primary generated charges, and the second half relaxes
by the interlayer charge recombination. The resulting state with a
porphyrin cation and electron in TiO<sub>2</sub> has an extremely
long lifetime and recombines with an average time constant of 23 ms
Effect of Mutual Position of Electron Donor and Acceptor on Photoinduced Electron Transfer in Supramolecular ChlorophyllâFullerene Dyads
In
this study we have explored the influence of mutual position
of chlorin electron donor and fullerene C<sub>60</sub> electron acceptor
on photoinduced electron transfer. Two zinc-chlorin-aza-[18]Âcrown-6
compounds and three pyrrolidino[60]Âfullerenes with alkyl aminium and
varying coordinative moieties were synthesized and used for self-assembling
of a set of complexes via two-point binding. The aza[18]Âcrown6 moieties were connected to chlorins via
amide linker either at 13<sup>4</sup> or 17<sup>4</sup> position,
hence, being attached on different sides of the chlorin plane. Furthermore,
in the former case, the linker holds the crown closely spaced, whereas,
in the latter, the linker gives more space and conformational freedom
for the crown with respect to the chlorin macrocycle. The coordinative
moieties at fullerene site, 3-pyridine, 4-pyridine, and 3-furan, were
built by utilizing the Prato reaction. The two-point binding drove
the molecules into specific complex formation by self-assembling;
aminium ion was chelated by crown ether, while zinc moiety of chlorin
was coordinated by pyridine and furan. Such pairing resulted in distinct
supramolecular chlorin-fullerene dyads with defined distance and orientation.
The performed computational studies at DFT level in solution, with
TPSS-D3/def2-TZVP//def2-SVP, indicated different geometries and binding
energies for the self-assembling complexes. Notably, the computations
pointed out that for all the studied complexes, the donorâacceptor
distances and binding energies were dictated by chirality of pyrrolidino
ring at C<sub>60</sub>. The selective excitation of chlorin chromophore
revealed efficient emission quenching in all dyads. The ultrafast
spectroscopy studies suggested a fast and efficient photoinduced charge
transfer in the dyads. The lifetimes of the charge separated states
range from 55 to 187 ps in <i>o</i>-dichlorobenzene and
from 14 to 60 ps in benzonitrile. Expectedly, the electron transfer
rate was found to be critically dependent on the donorâacceptor
distance; additionally, the mutual orientation of these entities was
found to have significant contribution on the rate
Exclusive occurrence of photoinduced energy transfer and switching of its direction by rectangular pi-extension of nanographenes
As structure defined cutouts of the graphene lattice, nanographene molecules have gained plenty of attention because of their high potential for versatile applications in organic electronics and energy conversion devices and as ideal model systems for the better understanding of intrinsic structureâproperty correlations of graphenes. In this study, well-defined nanographenes with sp2 carbon networks of different sizes, hexa-peri-hexabenzocoronene (HBC) and its rectangularly Ï-extended version, a short graphene nanoribbon (GNR), have been covalently functionalized with photoactive porphyrin molecules. On the basis of their spectroscopic studies, the photodynamics of the porphyrin-linked nanographenes was found to be influenced substantially by the size of the nanographenes. Photoexcitation of the porphyrinâHBC linked system led to exclusive energy transfer (EnT) from the first singlet excited state (S1) of the nanographene to the porphyrin, whereas opposite selective EnT occurred from the first and second singlet excited states (S1 and S2) of the porphyrin to the nanographene in the porphyrinâGNR linked system. In particular, ultrafast efficient EnTs from both the S2 and S1 states of the porphyrin to GNR mimic the corresponding ultrafast EnTs from the S2 and S1 states of carotenoids to chlorophylls in light-harvesting systems of natural photosynthesis. Such unique photophysical properties will be useful for the rational design of carbon-based photofunctional nanomaterials for optoelectronics and solar energy conversion devices