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Multicomponent supramolecular assembly systems enable the generation of materials with outstanding properties, not obtained from single-component systems, via a synergetic effect. Herein, we demonstrate a novel supramolecular coassembly system rendering highly ordered quantum dot (QD) arrangement structures formed via the self-assembly of azobenzene derivatives, where the photocontrollable photoluminescence (PL) properties of the QDs are realized based on photoisomerization. Upon mixing the assembled azobenzene derivatives and QDs in apolar media, a time-evolution coaggregation into hierarchical nanosheets with a highly ordered QD arrangement structure occurs. Upon photoirradiation, the nanosheets transform into ill-defined aggregates without arranged QDs together with enhancing the PL intensity. In days, the photoirradiated coaggregates undergo recovery of the PL properties corresponding to the arranged QDs through thermal isomerization.

Here, we report the solvent dependence of the photoinduced anion exchange reaction of cesium lead halide perovskite nanocrystals (NCs) in solutions containing halomethane solvents such as CHCl3. Th...

Photoluminescence (PL) on/off switching systems using photochromic molecules have a high potential for a wide range of applications, such as optical memories, chemo- and biosensing, and superresolu...

Colloidal semiconductor nanocrystals, known as quantum dots (QDs), are regarded as brightly photoluminescent nanomaterials possessing outstanding photophysical properties, such as high photodurability and tunable absorption and emission wavelengths. Therefore, QDs have great potential for a wide range of applications, such as in photoluminescent materials, biosensors and photovoltaic devices. Since the development of synthetic methods for accessing high-quality QDs with uniform morphology and size, various types of QDs have been designed and synthesized, and their photophysical properties dispersed in solutions and at the single QD level have been reported in detail. In contrast to dispersed QDs, the photophysical properties of assembled QDs have not been revealed, although the structures of the self-assemblies are closely related to the device performance of the solid-state QDs. Therefore, creating and controlling the self-assembly of QDs into well-defined nanostructures is crucial but remains challenging. In this Minireview, we discuss the notable examples of assembled QDs such as dimers, trimers and extended QD assemblies achieved using organic templates. This Minireview should facilitate future advancements in materials science related to the assembled QDs.

Most azobenzene derivatives are utilized as well-defined photoresponsive materials, but their emission properties have not been of great interest as they are relatively poor. Here, we report crystallization-induced emission (CIE) based on the suppression of the photoisomerization of azobenzene derivatives. Although these molecules show negligible emission in solution, their microcrystals exhibit intense emission from the azobenzene moieties as a result of CIE. Upon rapid precipitation, fine particles with low crystallinity were kinetically formed and underwent CIE over time with a concomitant increase in crystallinity. Furthermore, we demonstrated "photocutting" of an emissive single crystal using a strong laser by a combination of CIE behavior and photomelting based on the photoisomerization of the azobenzene moiety. Our results regarding the CIE behavior of azobenzene derivatives in addition to their photoisomerization can provide a new platform for developing photoresponsive luminescent materials.

Supramolecular assemblies have been extensively studied because of their fundamental insights into intermolecular interactions and their potential applications to optoelectronic devices. Among vari...

The formation of well-defined nanostructures comprising assembled semiconductor quantum dots (QDs) is a challenging research task. Recently, we found that the introduction of π-conjugated molecules...

The photo-induced generation of unstable molecules generally requires stringent conditions to prevent oxidation and the concomitant decomposition of the products. The visible-light-induced conversion of two heptacene precursors to heptacene was studied. Single crystals of bis- and mono-α-diketone-type heptacene precursors (7-DK2 and 7-DK1, respectively), were prepared to investigate the effect of precursor structure on reactivity. The photoirradiation of a 7-DK2 single crystal cleaved only one α-diketone group, forming an intermediate bearing a pentacene subunit, while that of a 7-DK1 single crystal gave rise to characteristic absorption peaks of heptacene and their increase in intensity with photoirradiation time, indicating the generation of heptacene without decomposition. Heptacene production was not observed when the precursors were photoirradiated in solution, implying that the single crystal interior provided isolation from the external environment, thus preventing heptacene oxidation.

Recently, we revealed that 6,13-dihydro-6,13-ethanopentacene-15,16-dione (PDK) could be quantitatively photoconverted into pentacene even in the crystal phase, accompanied by the destruction of the crystals. In this work, we investigated the relationship between the photoinduced morphological changes and the light intensity for the photoconversion at a single micrometre-sized crystal level. Photoirradiation with a strong intensity (over 100 kW cm-2) resulted in hole formation in a single crystal. When medium intensity (0.5-100 kW cm-2) was irradiated, destruction including separation and jumping of the crystal was observed. Absorption spectrum measurement of the single crystal revealed that when almost same number of pentacene was generated, the destruction was induced by the generated strain within crystal due to the stacking mismatch between the different molecules. Upon photoirradiation with a low intensity (below 0.5 kW cm-2), protruding pillar objects were observed on the crystal surface. This formation is a result of the surface movement of molecules through the relaxation of strain. Our results provide important insight into stimuli-responsive crystal materials and could contribute to the generation and application of remotely controllable smart materials.

Colloidal semiconductor nanocrystals, so-called quantum dots (QDs), are attractive as molecular-like smart nanomaterials, and their emission and optoelectronic properties in the dispersed state have been actively studied. The construction of supramolecular structures composed of multiple QDs, however, is still challenging. Here, a new strategy to form supramolecular QD structures via self-assembly of perylene bisimide (PBI) dyes is demonstrated. In a mixed solution, QDs and PBI undergo time-dependent fusion to form an isolated colloidal QD-PBI complex or a unique QD-PBI co-aggregate composed of QDs arranged along a sheet-like PBI nanostructure, and these dramatically different supramolecular structures can be controlled by the solvent polarity.

Postsynthesis anion-exchange reaction of cesium lead halide (CsPbX3; X = Cl, Br, and I) perovskite nanocrystals (NCs) has emerged as a unique strategy to control band gap. Recently, the partially a...

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using a silver-coated atomic force microscopy tip (AgTip) as the plasmonic nanostructure. Using the AgTip, which exhibited a well-defined localized surface plasmon (LSP) resonance band, we controlled the spectral overlap and the distance between the single NQD and the AgTip. The emission behavior of the single NQD when approaching the AgTip at the nanometer scale was measured using off-resonance (405 nm) and resonance (465 nm) excitation of the LSP. We directly observed the conversion of the single-photon emission from a single NQD to multiphoton emission with reduction of the emission lifetime at both excitation wavelengths as the NQD-AgTip distance decreased, whereas a decrease and increase in the emission intensity were observed at 405 and 465 nm excitation, respectively. By combining theoretical analysis and the numerical simulation of the AgTip, we deduced that the enhancement of the multiphoton emission was caused by the quenching of the single-exciton state due to the energy transfer from the NQD to the AgTip and that the emission intensity was increased by enhancement of the excitation rate due to the electric field of the LSP on the AgTip. These results provide evidence that the photon statistics and the photon flux from the single NQD can be manipulated by the plasmonic nanostructure through control of the spectral overlap and the distance.

Tetraalkylpentacenes having alkyl chains at 2,3,9,10-positions (Et-PEN, Pr-PEN and Hex-PEN) were prepared from their precursors Et-PDK, Pr-PDK and Hex-PDK, respectively. Photoreactions proceeded both in solutions, thin-films, and crystals, thus the properties of Et-PDK in films can be studied despite the instability of the pentacenes in solution. Et-PEN showed significantly different aggregation-nature compared with the parent pentacene. The hole mobilities of Et-PEN and Pr-PEN in films were 3.4 [times] 10-6 and 8.1 [times] 10-7 cm2 V-1 s-1, respectively, determined by space-charge-limited current measurement, comparable with the order 10-6 cm2 V-1 s-1 of the electron mobility of Alq3.

The photon antibunching behavior in the photoluminescence (PL) of single CdSe/ZnS semiconductor nanocrystals (NCs) interacting with the localized surface plasmon resonance (LSPR) of Ag nanostructure was investigated using fs-pulsed laser excitation at two excitation wavelengths. The time traces of the PL intensity, the PL decay curves, and the photon correlations of single NCs on a rough Ag film and on a coverslip were measured simultaneously, and an increase in the PL intensity accompanied by shortening of the PL lifetime was observed for the single NCs on the rough Ag film. The enhancement factor of the PL intensity depended on the excitation wavelength. Nearly all of the single NCs with enhanced PL exhibited photon antibunching behavior independent of the enhancement factor. Based on the enhanced radiative- and nonradiative-decay rates estimated from the experimental data, the mechanism of the photon antibunching behavior was considered as follows. To exhibit the photon antibunching behavior, the nonradiative Auger recombination between the generated excitons in a single NC is important. When the radiative- and the nonradiative-decay rates enhanced by the LSPR are faster than the Auger recombination rate, the probability of photon antibunching decreases. However, such fast radiative- and the nonradiative decay rates were not observed for single NCs interacting with the LSPR of the rough Ag film in this work. Therefore, the PL intensity from a single NC can be increased while maintaining the photon antibunching behavior. Our findings assist in the creation of effective single-photon sources and provide important information on the emission properties of an NC coupled with the plasmon of a metal nanostructure.

Extremely pure polymer matrices were used for elucidating the fluorescence properties of singly isolated charge-transfer (CT) complexes formed between the donor N-ethylcarbazole and the acceptor 1,2,4,5-tetracyanobenzene. Simultaneous measurements (time traces of CT fluorescence intensities and lifetimes) using single-molecule fluorescence spectroscopy showed three patterns: (1) fluctuations in the fluorescence intensities and lifetimes seldom occurred, (2) the fluorescence intensities frequently fluctuated together with the lifetimes, or (3) in addition to the above fluctuations with time, blinking and/or off-states longer than 1 s were observed. For methacrylate polymers, both the degree of fluctuations in the CT fluorescence lifetimes and the percentage of the CT complexes showing off-states increased with the free volume of the host polymers. These results suggest that the degree of fluctuations in the relative geometrical arrangements of the donor and acceptor molecules is related to the availability of space in the host polymer, and that the free volume provides the necessary space for formation of non-fluorescent donor–acceptor geometries of the CT complexes and/or temporal dissociation of the CT complexes. Survival times of the CT fluorescence were also closely related with the free volume of the host polymers.

To reveal the exciton dynamics, particularly multiexciton dynamics in single colloidal CdSe/ZnS quantum dots (QDs) interacting with the localized surface plasmon resonance (LSPR) of silver nanoparticles (AgNPs), we investigated the single-photon emission behavior in the fluorescence from the single QDs using a single-molecule spectroscopy technique in combination with a femtosecond-pulsed laser excitation. By applying simultaneous measurements of the photon-correlation (photon antibunching), the fluorescence intensity, and the fluorescence lifetime to the single QD near AgNPs, we revealed that the probability of single-photon emission strongly depended on the fluorescence lifetime; that is, the probability of single-photon emission decreased when the lifetime was shorter than subnanoseconds. On the basis of the estimation of both radiative and nonradiative decay rates enhanced by the LSPR, the following mechanism was suggested. In the absence of AgNPs, multiple excitons generated by a high-power excitatio...

Single molecule fluorescence spectroscopy (SMS) was used to elucidate the fluorescence dynamics of singly isolated charge-transfer (CT) complexes formed between various monocarbazolyl and dicarbazo...

Single-photon behavior in the emission from a single nanoparticle consisting of a single poly[2-methoxy-5-(2′-ethylhexyloxy)- p -phenylene vinylene] (MEH-PPV, molecular weight: 2,600,000 amu) chain has been investigated. Photon correlation measurements of a number of single nanoparticles revealed that the probability of single-photon emission from the single nanoparticles clearly increases, compared with that of single chains embedded in host polymer matrices, poly(methyl methacrylate) (PMMA) and polystyrene (PS). The result suggested that even a single MEH-PPV chain with high molecular weight, which does not exhibit single-photon emission in PMMA and PS, is forced to exhibit single-photon emission by adopting “compact” chain conformation like nanoparticle. Efficient exciton migration and exciton annihilation processes in the compact chain conformation most probably result in the efficient single-photon emission from the single nanoparticle. The present results indicate that multi-quantum systems consisting of a large number of chromophores, such as the MEH-PPV, can be made to behave as single-photon sources by appropriately controlling their size.

4-Cyano-4′-(1-(1-pyrenyl)- n -octyloxy)biphenyl (8OCBPy), where the hydrogen atom of a well-known mesogen 4-cyano-4′- n -octyloxybiphenyl (8OCB) is substituted with one pyrenyl (Py) chromophore, was synthesized. When 8OCBPy was doped in the mesophases of the similar mesogen of 4-cyano-4′- n -decyloxybiphenyl (10OCB), the Py chromophores should be oriented by a constraint in the mesophases as compared with free chromophores dispersed in the mesophases. The binary mixture exhibited smectic A (Sm A) and nematic (N) mesophases. The mesophases and isotropic (I) phase of the binary mixture exhibited excimer as well as monomer fluorescence. The intermolecular excimer formation-dissociation kinetics of 8OCBPy in the Sm and I phases of its binary mixture was investigated in comparison with that for a 1-ethylpyrene binary system. Positive enthalpy and entropy changes for the excimer formation were found in the Sm A mesophase, whereas their usual changes were found in the I phase. These anomalous phenomena observed in the Sm A mesophase were interpreted by the entropy-controlled excimer formation associated with the decrease in ordering of the 10OCB-mesogen molecules around the 8OCBPy arranged in the Sm A layers.

We report the photoluminescence properties of polymer alternating multilayer films containing a fluorescent dye in one component. The alternating multilayer film with periodicity in both refractive indices and dye distribution showed 6 times higher intensity of amplified spontaneous emission than the multilayer film with periodicity in dye distribution only. Multilayer films that have a structure of Fabry–Perot resonator showed a lasing threshold of approximately 1.7 mJ cm − 2 .

We prepared nanoparticles of an organic dye, acridine orange (AO), dispersed in poly(methacrylic acid) (PMA) films by spin-coating the solution of the two components. The surface of the AO/PMA films became bumpier with increasing AO concentration (cAO). The absorption and fluorescence spectra of AO/PMA films exhibited a marked dependence on cAO at low cAO (cAO 2.1 × 10− 1 mol kg− 1). The peak shift of fluorescence spectra with changing cAO was as large as ∼ 100 nm.

The site-selective doping of dyes into spin-cast thin films with different phase separation structures of polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) diblock copolymers and the dopant-induced laser ablation of the dye-doped films fabricated were investigated. The selective doping of dyes into P4VP parts was carried out by immersing the films in a methanol solution containing the dyes, in which the driving force was induced by hydrogen bonds between the nitrogen atoms of pyridyl groups and the carboxylic groups of the dyes. Schematic models for the adsorption process of the dyes in the methanol solution were discussed. Dopant-induced laser ablation was carried out on the dye-doped block copolymer films, resulting in the ablation of dye-doped P4VP parts only. Factors affecting selective ablation, such as dyes, the morphologies of phase separation structures, the number-average molecular weights of the diblock copolymers, and irradiation environments, were discussed.

4-Cyano-4′-(1-( N -carbazolyl)- n -octyloxy)biphenyl (8OCBCz), where the hydrogen atom of a well-known mesogen 4-cyano-4′- n -octyloxybiphenyl (8OCB) is substituted with one carbazolyl (Cz) chromophore, was synthesized, and the photophysical and photoconductive properties of its neat form and its binary mixtures with 4-cyano-4′- n -decyloxybiphenyl (10OCB) were investigated. The 8OCBCz exhibited intermolecular exciplex fluorescence in concentrated solutions. When 8OCBCz was quenched from its molten state, it formed an amorphous state, which exhibited exciplex fluorescence and transient photocurrent signals of both the positive and negative charge carriers. However, their mobilities could not be determined because of the strongly dispersive signals. The mixtures exhibited smectic A (Sm A) and nematic (N) mesophases. These mesophases and the isotropic phase exhibited exciplex as well as monomer fluorescence. The exciplex formation mechanism in the Sm A mesophase differed from those in the N and isotropic phases. The transient photocurrent signals for both the positive and negative charge carriers were also observed for the binary mixtures. Ionic conduction was suggested for the N and isotropic phases, whereas electronic conduction was suggested for the Sm A mesophase. The ionic carrier species were proposed.

Laser irradiation using a Nd3+:YAG laser (532 nm, 8 ns, 10 Hz) on an ethanol suspension of micrometer-sized pentacene crystals induced absorption spectral changes in the solution, as a result of the formation of pentacene nanoparticles. The nanoparticles were platelike crystals. The nanoparticles formed by irradiation with a fluence of 50 mJ/cm2 for 30 min were 4–13 nm in height and 10–70 nm in width. The threshold laser fluence for the formation was determined to be ca. 20 mJ/cm2, and irradiation with fluences above 80 mJ/cm2 induced the decomposition of the pentacene nanoparticles. The nanoparticle size decreased with an increase in the laser fluence, which was reflected in the longest-wavelength peak position of the absorption bands of the pentacene nanoparticles. On the basis of these results, the mechanism of pentacene nanoparticle formation by laser irradiation is discussed in connection with those of vanadyl phthalocyanine and quinacridone systems reported by Masuhara and coworkers [J. Phys. Chem. A 106 (2002) 2135; Jpn. J. Appl. Phys. 42 (2003) 2725; Jpn. J. Appl. Phys. 45 (2006) 384].

Real-time measurement of the catalysis and substrate kinetics of a single-enzyme hydrolysis reaction is demonstrated with confocal fluorescence microscopy (CFM; see picture, green = CFM beam). A single lipase is shown to have a broad range of conformations; each conformation contributes to the overall enzymatic activity, an observation that is often masked by ensemble measurements.

The spectroscopic properties of seven varieties of wire-type dendrimers, which consist of different generation numbers of dendritic wedges and molecular weights, were examined in tetrahydrofuran solution, in the solid state, and in good/poor solvent mixture for the purpose of revealing the relation between molecular conformation and spectral behavior. The second and third generation wire-type dendrimers showed a sharp aggregate band, which is ascribed to the interchain π stacked aggregate, in the solid state and in the good/poor solvent mixture, while the fourth generation wire-type dendrimer did not show the aggregate band. The absence of the aggregate band indicates that the bulky fourth generation dendritic wedges prevent the conjugated backbone from forming the interchain π stacked aggregate even in the solid state and in the good/poor solvent mixture. In the experiment on poor solvent-induced aggregation, we observed the progressive spectral change in the process of forming the aggregate, and simulta...

Laser manipulation and laser trapping techniques were applied to μm sized gel-like wire-type dendrimer (L3PPE130 and L4PPE8) assemblies, which are formed at drying process of their tetrahydrofuran (THF) solution on a glass substrate. Deformation and extension of single gel-like assemblies were demonstrated with irradiation of a focused 1064 nm laser beam by scanning a microscope stage. In repetitive irradiation experiments, contraction and swelling of the gel-like assembly were observed in response to the switch on and off of the laser beam, respectively, and in the case of the L3PPE130 gel-like assembly, fluorescence spectra detected at a focal point changed accompanying the contraction and swelling behavior. This spectral change means molecular aggregates were formed transiently by photon pressure of the focused near-infrared laser beam.

The photoconversion of a crystalline-phase precursor, 6,13-dihydro-6,13-ethanopentacene-15,16-dione (PDK), into pentacene was examined. Upon irradiation with 470 nm light, the photoconversion proceeded even in the crystalline phase. Although the rate of the crystalline phase photoconversion was much slower than that in solution, quantitative photoconversion was achieved upon lengthy photoirradiation. The photoconversion of PDK was also confirmed at the single μm-sized crystal level by observing fluorescence images and spectra of the PDK crystal using confocal microscopy. Destruction of the crystal was observed when some of the PDK molecules in the crystal were photoconverted into pentacene. These results indicate that the crystalline-phase photoconversion of PDK proceeded through the destruction of the crystal. Quantitative photoconversion was achieved as a result.

Photon-correlation measurements were applied to single chains of poly[2-methoxy-5-(2-ethylhexyloxy)-p-phenylene vinylene] of various molecular weights in a fluid solvent in order to investigate the...

Solvents with limited solubility for N,N'-di(octyl)perylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C8) were used for laser ablation in liquid. Laser irradiation of the suspension induced an absorption spectral change of the solution. The absorbance of free PTCDI-C8 molecules in the solution obtained by laser irradiation was unusually larger than that of the suspension before laser irradiation, suggesting that a supersaturated solution was formed by laser irradiation of PTCDI-C8 nanoparticles prepared by laser ablation.

Novel bisimide-fused acenes were synthesized viabismuth triflate mediated double-cyclization reaction of acid chlorides and isocyanates. Their optical and electrical properties revealed significantly smaller HOMO–LUMO gaps compared with those of their parent acenes. Fabricated OFET based on tetracene bisimide showed n-type OFET outputs.

Novel bisimide-fused acenes were synthesized via bismuth triflate mediated double-cyclization reaction of acid chlorides and isocyanates. Their optical and electrical properties revealed significantly smaller HOMO-LUMO gaps compared with those of their parent acenes. Fabricated OFET based on tetracene bisimide showed n-type OFET outputs.

Single-molecule techniques offer a unique tool for studying the dynamical behavior of individual molecules and provide the possibility to construct distributions from individual events rather than from a signal stemming from an ensemble of molecules. In biological systems, known for their complexity, these techniques make it possible to gain insights into the detailed spectrum of molecular conformational changes and activities. Here, we report on the direct observation of a single lipase-catalyzed reaction for extended periods of time (hours), by using confocal fluorescence microscopy. When adding a profluorescent substrate, the monitored enzymatic activity appears as a trajectory of “on-state” and “off-state” events. The waiting time probability density function of the off state and the state-correlation function fit stretched exponentials, independent of the substrate concentration in a certain range. The data analysis unravels oscillations in the logarithmic derivative of the off-state waiting time probability density function and correlations between off-state events. These findings imply that the fluctuating enzyme model, which involves a spectrum of enzymatic conformations that interconvert on the time scale of the catalytic activity, best describes the observed enzymatic activity. Based on this model, values for the coupling and reaction rates are extracted.

We use single-molecule fluorescence lifetimes to probe dynamics of photoinduced reversible electron transfer occurring between triphenylamine (donor) and perylenediimide (acceptor) in single molecules of a polyphenylenic rigid dendrimer embedded in polystyrene. Here, reversible electron transfer in individual donor-acceptor molecules results in delayed fluorescence that is emitted with a high photon count rate. By monitoring fluorescence decay times on a photon-by-photon basis, we find fluctuations in both forward and reverse electron transfer spanning a broad time range, from milliseconds to seconds. Fluctuations are induced by conformational changes in the dendrimer structure as well by polystyrene chain reorientation. The conformational changes are related to changes in the dihedral angle of adjacent phenyl rings located in the dendritic branch near the donor transferring the charge, a torsional motion that results in millisecond fluctuations in the “through-bond” donor-acceptor electronic coupling. Polymer chain reorientation leads to changes in the local polarity experienced by the donors and to changes in the solvation of the charge-separated state. As a result, switching between different donor moieties within the same single molecule becomes possible and induces fluctuations in decay time on a time scale of seconds.

Using single molecule fluorescence spectroscopy we have investigated fluorescence resonance energy transfer (FRET) occurring between two peryleneimide (PI) chromophores in a series of synthetic systems: PI end-capped fluorene trimers, hexamers and polymers for which the interchromophoric distance vary from 3.4 to 5.9 and 42 nm, respectively. By monitoring in parallel the fluorescence intensity and the number of independent emitting chromophores from each molecule, we could discriminate between competitive Foerster-type energy transfer processes such as energy hopping, singlet-singlet annihilation and singlet-triplet annihilation for the PI end-capped fluorine compounds. Due to different energy transfer efficiencies, variations in the interchromophoric distance enable switching between these processes. The single molecule fluorescence data reported here suggest that similar energy transfer pathways have to be considered in the analysis of single molecule trajectories of donor/acceptor pairs, as well as in the case of more complex systems like natural multichromophoric systems, such as light harvesting antennas or oligomeric fluorescent proteins.

Single-molecule fluorescence spectroscopy was performed on a number of multi-peryleneimide substituted polyphenylene dendrimers for the purpose of investigating the parameters which influence the efficiency of the dendrimers as single-photon sources at room temperature. Analysis of fluorescence intensity, lifetime, and interphoton arrival time distribution revealed that all measured first-generation dendrimers behave as single-photon emitters when more than one chromophore is excited by a single excitation pulse regardless of the number of constituent chromophores. This is a result of efficient singlet-singlet annihilation, which becomes less efficient in higher-generation dendrimers when the interchromophoric distance increases. The efficiency of the investigated dendrimers as single-photon sources depends on several other parameters, such as the nature of the surrounding polymer matrix, the number of chromophores, and the extent of interchromophoric interactions. These parameters mainly affect the frequency of singlet-triplet annihilation, which in turn dominates the quality of these multichromophoric dendrimers as single-photon sources. The results reported here are important not only for the design of single-photon sources based on single organic molecules but also for a fundamental understanding of natural and artificial multichromophoric systems.

Time-resolved photoluminescence (PL) and transient absorption (TA) spectroscopy are conducted in order to get knowledge on the excited state of CdSe nanorods (NR), and to assess the impact of Au nanoparticles (NP) on the carrier dynamics of hybrid Au-CdSe NRs. The decay dynamics measured in solution show an increase of non-radiative decay channels in the presence of Au NPs, whose characteristic lifetimes vary from a few ps to tens of ps. The ultrafast electron transfer from CdSe NRs to Au NPs efficiently competes with intraband relaxation dynamics, allowing observation of the hot-electron transfer process. Furthermore, the time-averaged PL decay of CdSe NRs shows a strongly multiexponential feature that was analyzed by single-particle spectroscopy. The PL decay of individual NRs fluctuates in time and is correlated with the PL intensity. We show that the time-averaged decay of bare CdSe NRs is composed of (i) a long lifetime component corresponding to bright CdSe NRs (ON state) and (ii) a short lifetime component corresponding to charged NRs that open additional fast non-radiative channels (OFF state). When Au NPs are attached to CdSe NRs, the ON state PL decays still show a long lifetime component, suggesting that the length of the NRs may hinder electron transfer if the exciton is formed far from the Au NPs. Finally, quantitative analysis of the OFF state decays shows that electron transfer occurs even in the presence of fast non-radiative pathways in charged systems.

The influence of molecular weight (MW) and chain conformation on single-photon emission from isolated chains of poly[2-methoxy,5-(2′-ethylhexyloxy)-p-phenylene-vinylene] have been investigated. The probability of single-photon emission clearly increased with decreasing MW, and when the polymer chains adopted the “collapsed” conformation, this probability was larger than for the “extended” conformation. Even single polymer chains of high MW behaved as single-photon sources by adopting the collapsed conformation. These results indicate that multi-quantum systems consisting of a large number of chromophores can be made to behave as single-photon sources by appropriately controlling their size.

Dopant-induced laser ablation was applied to thin polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer films doped selectively with tetrakis(4-carboxyphenyl)porphine (TCPP) into the nanoscale spherical domain of P4VP-island parts. Under dry-film conditions, the ablation of the island parts was not induced. On the other hand, in methanol solvent, only the P4VP-island parts doped with TCPP were ablated selectively. The dopant-induced laser ablation is attributed to the fact that the P4VP-island parts are in the swollen state, where P4VP chains cross-linked by TCPP-dopant molecules exist with a high density in methanol. This is the first report concerning the site-selective laser ablation of diblock copolymer films.