A perylene-3, 4∶9, 10-bis(dicarboximide)-based electron donor-acceptor monomer was designed to selfassemble using the synergistic effects of ð-ð stacking, microsegregation, and hydrogen bonding. The resulting aggregates were characterized in solution by small-angle X-ray scattering (SAXS), while the solid-state structure was probed by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. The solution-phase assemblies were found to consist of 12 monomers arranged in either a face-to-face stacked pair of hydrogen-bonded hexagonal arrays or a two-turn helix. The SAXS data do not allow a clear distinction between these two cyclic motifs. These cyclic arrays grow to lengths of about 1m and form bundles of cylindrical structures in the solid phase. Aggregation is solvent dependent, with methylcyclohexane inducing aggregation and tetrahydrofuran disrupting it. The solutionphase photophysics of the dodecamer were probed by UV-vis, time-resolved fluorescence, and femtosecond transient absorption spectroscopies, revealing that formation of the dodecamer introduces an ultrafast electron-transfer pathway that is not present in the monomer.

Amphiphilic phthalocyanines with one crown ether and three alkyl chain substitutions can form stable monolayers on a water surface. This monolayer can be transferred to a substrate by a vertical dipping method. The arrangement of phthalocyanine molecules in LB films was affected by the length of alkyl chains and the coordination of alkali ions in crown ether. Davydov splitting was observed in the absorption spectra of the LB films of phthalocyanine with the shortest alkyl chain substitutions, and this splitting was affected by the alkali ions in the subphase.

A series of novel tetra-substituted naphthalocyanines featuring hydroxy and carboxylate substituents in peripheral positions have been synthesised in reasonable yields and characterised by spectroscopic techniques. The photochemical properties of the tetra-acid derivative 7 were examined following immobilisation on a nanocrystalline TiO2 surface and photoinduced dye cations were observed following optical excitation. 7 has a redox potential of 0.25 V (vs. Ag/AgCl), which is lower than is required for an efficient regeneration reaction and, therefore, results in limited photocurrent flow when 7 is used in photoelectrochemical solar cells.

The adenine-containing zinc(II) phthalocyanines 3, 4a, and 4b have been prepared by standard O-alkylation of the tetrahydroxy analogue 1. These macrocycles exhibit rather strong intermolecular interactions resulting in a poor solubility in organic solvents and unusual spectral properties that are highly solvent-dependent. Self-assembly of the tetra-adenine phthalocyanine 3 and the thymine-containing 9, 10-anthraquinone 6 through the Watson-Crick base-pairing interactions has also been demonstrated by fluorescence quenching experiments.