Novel organic solar cells have been prepared using molecular clusters of porphyrin dendrimer (donor) and fullerene (acceptor) dye units assembled on SnO2 electrodes. The molecular clusters of porphyrin with dendritic structure and fullerene exhibit controlled size and shape in contrast with the reference systems (a porphyrin dimer and a porphyrin−fullerene dyad) without dendritic structure in TEM images, which show rather irregular and smaller clusters. The composite molecular nanoclusters of dendritic porphyrin and fullerene prepared in acetonitrile/toluene mixed solvent absorb light over entire spectrum of visible light. The comparison of photoelectrochemical properties of composite molecular cluster of porphyrin and fullerene with that of molecular cluster of porphyrin−C60 dyad with covalent linkage shows the importance of interpenetrating structure in each network to transport hole and electron efficiently. Furthermore, organic photovoltaic cells using clusters of supramolecular complexes of V-shaped porphyrin dimer and porphyrin dendrimers with fullerene exhibit remarkable enhancement in the photoelectrochemical performance as well as broader photoresponse in the visible and near-infrared regions as compared with the reference system. This clearly indicates that the π−π interaction between porphyrins and fullerenes in the supramolecular clusters plays an important role in improving the light energy conversion efficiency.

A series of electron donor−acceptor (DA) dyads, composed of a porphyrin donor and a fullerene acceptor covalently linked with two molecular chains, were used to fabricate solid molecular films with the Langmuir−Blodgett (LB) technique. By means of the LB technique, the DA molecules can be oriented perpendicular to the plane of the substrate. In DHD6ee and its zinc derivative hydrophilic groups are attached to the phenyl moieties in the porphyrin end of the molecule; while in the other three dyads, TBD6a, TBD6hp, and TBD4hp, the hydrophilic groups are in the fullerene end of the molecule. This makes it possible to alternate the orientation of the molecules in two opposite directions with respect to the air−water interface and to fabricate molecular assemblies in which the direction of the primary photoinduced vectorial electron transfer can be controlled both by the deposition direction of the LB monolayer and by the selection of the used DA molecule. This was proved by the time-resolved Maxwell displacement charge measurements. The spectroscopic properties of the DA films were studied with the steady-state absorption and fluorescence methods. In addition, the time correlated single photon counting technique was used to determine the fluorescence properties of the dyad films.

accelerating voltage. Samples for TEM were prepared by dispersing the powdered sample in ethanol by sonication and then drop-drying on a copper grid (400 mesh, electron microscopy sciences) coated with carbon film. High-resolution TEM images were obtained with a JEOL-2010 microscope. SAEDS measurements were performed using a 25 nm electron beam attached with a JEOL-2010 TEM instrument. The AFM images of the sample loaded on a Si substrate were obtained using a Digital Instruments 3100 dimension AFM operating in non-contact mode. The DC magnetic measurements in the temperature range 5±100 K were performed in a commercial (Quantum Design) super-conducting quantum-interference device (SQUID) magnetometer.

The ultrafast electron transfer occurring upon Soret excitation of three new porphyrin-ferrocene (XP-Fc) dyads has been studied by femtosecond up-conversion and pump-probe techniques. In the XP-Fc dyads (XP-Fcs) designed in this study, the ferrocene moiety is covalently bonded to the meso positions of 3,5-di-tert-butylphenyl zinc porphyrin (BPZnP-Fc), pentafluorophenyl zinc porphyrin (FPZnP-Fc), and 3,5-di-tert-butylphenyl free-base porphyrin (BPH2P-Fc). Charge separation and recombination in the XP-Fcs were confirmed by transient absorption spectra, and the lifetimes of the charge-separated states were estimated from the decay rate of the porphyrin radical anion band to be approximately 20 ps. The charge-separation rates of the XP-Fcs were found to be >10(13) s-1 from the S2 state and 6.3x10(12) s-1 from the S1 state. Charge separation from the S2 state was particularly efficient for BPZnP-Fc, whereas the main reaction pathway was from the S1 state for BPH2P-Fc. Charge separation from the S2 and S1 states occurred at virtually the same rate in benzene and tetrahydrofuran and was much faster than their solvation times. Analysis of these results using semiquantum Marcus theory indicates that the magnitude of the electronic-tunneling matrix element is rather large and far outside the range of nonadiabatic approximation. The pump-probe data show the presence of vibrational coherence during the reactions, suggesting that wavepacket dynamics on the adiabatic potential energy surface might regulate the ultrafast reactions.

Substituent effects of porphyrin on the structures and photophysical properties of the J-aggregates of protonated 5-(4-alkoxyphenyl)-10,15,20-tris(4-sulfonatophenyl)porphyrin have been examined for the first time. Selective formation of the porphyrin J-aggregate was attained when suitable length of the alkoxy group was employed for the amphiphilic porphyrin. Namely, a regular leaflike structure was observed for the J-aggregates of protonated 5-(4-octyloxyphenyl)-10,15,20-tris(4-sulfonatophenyl)porphyrin, which was consistent with the results obtained by using the UV-visible absorption and dynamic light-scattering measurements. A bilayer structure in which the hydrophobic alkoxyl groups facing inside the bilayer are interdigitated to each other, whereas the hydrophilic porphyrin moieties are exposed outside, was proposed to explain the unique porphyrin J-aggregate. Fast energy migration and efficient quenching by defect site in the J-aggregates were suggested to rationalize the short lifetimes of the excited J-aggregates.

Systematic series of indium tin oxide (ITO) electrodes modified covalently with self-assembled monolayers (SAMs) of ferrocene-porphyrin-fullerene triads and porphyrin-fullerene dyads were designed to gain valuable insight into the development of molecular photovoltaic devices. The structures of SAMs on ITO have been investigated by UV/Vis absorption spectroscopy, atomic force microscopy, and cyclic voltammetry. The photoelectrochemical and photophysical (fluorescence lifetime and time-resolved transient absorption) properties were also determined. The highest quantum yield of photocurrent generation (11 %) among donor-acceptor linked systems which are covalently attached to the surface of ITO electrodes was achieved with SAMs of ferrocene-zinc porphyrin-fullerene linked triad on ITO electrodes. The quantum yields of photocurrent generation correlate well with the charge-separation efficiency and the lifetime of the charge-separated state of the porphyrin-fullerene linked systems in solution. These results provide valuable information for the construction of photonic molecular devices and artificial photosynthetic systems on ITO electrodes.

Multifullerene-terminated dendrimers Gn (n ) 1-5) were synthesized and structural, photophysical, and photoelectrochemical properties were studied for the fullerene dendrimers and their nanoclusters. The fullerene dendrimers formed clusters when toluene solutions of the fullerene dendrimers were injected into acetonitrile. Dynamic light scattering and atomic force and scanning electron microscopic measurements on these clusters revealed that the cluster size decreased with increasing the generation number of the dendrimers. The negatively charged clusters were deposited electrophoretically onto a nanostructured SnO 2 -coated ITO electrode by applying DC voltage to the electrode. Photoelectrochemical measurements were carried out in acetonitrile dissolved 0.5 M LiI and 0.01 M I 2 with the standard three electrodes containing the fullerene dendrimermodified SnO 2 working electrode, a platinum wire as a counter electrode, and I -/I 3 -as a reference electrode. An incident photon-to-photocurrent efficiency of the dendrimer photoelectrochemical devices increased with increasing the generation number. Such a close relationship between the structure and photophysical and photoelectrochemical properties of the fullerene dendrimers and their nanoclusters will provide knowledge of photophysics regarding photoactive molecular assemblies with dendritic architectures.

[structure: see text] The photovoltaic cell composed of both fullerene nanoclusters and 9-mesityl-10-carboxymethylacridinium ion exhibits significant enhancement in the photoelectrochemical performance as well as broader photoresponse in the visible and near-infrared regions as compared with the reference system containing only each component.