The synthesis, characterization, and stability of porphyrin nanoparticles of 20-200 nm diameter presented herein is general for meso arylporphyrins. The elegance of the method lies in its simplicity. This work shows that the agent used to prevent agglomeration can be covalently attached to the dye forming the particle or be part of the solvent system. It also demonstrates that these and other types of dyes with a range of photonic properties do not need to be prepared by inclusion in external matrices or by designed self-assembly a priori. The matrix may severely limit the functionality of the particles in the former case, and at present this size of particle is difficult to achieve via the latter.

Tessellation of nine free-base porphyrins into a 3 ؋ 3 array is accomplished by the self-assembly of 21 molecular entities of four different kinds, one central, four corner, and four side porphyrins with 12 trans Pd(II) complexes, by specifically designed and targeted intermolecular interactions. Strikingly, the self-assembly of 30 components into a metalloporphyrin nonamer results from the addition of nine equivalents of a first-row transition metal to the above milieu. In this case each porphyrin in the nonameric array coordinates the same metal such as Mn(II), Ni(II), Co(II), or Zn(II). This feat is accomplished by taking advantage of the highly selective porphyrin complexation kinetics and thermodynamics for different metals. In a second, hierarchical self-assembly process, nonspecific intermolecular interactions can be exploited to form nanoscaled three-dimensional aggregates of the supramolecular porphyrin arrays. In solution, the size of the nanoscaled aggregate can be directed by fine-tuning the properties of the component macrocycles, by choice of metalloporphyrin, and the kinetics of the secondary self-assembly process. As precursors to device formation, nanoscale structures of the porphyrin arrays and aggregates of controlled size may be deposited on surfaces. Atomic force microscopy and scanning tunneling microscopy of these materials show that the choice of surface (gold, mica, glass, etc.) may be used to modulate the aggregate size and thus its photophysical properties. Once on the surface the materials are extremely robust.

The incorporation of designed self-assembled supramolecular structures into devices requires deposition onto surfaces with retention of both structure and function. This remains a challenge and can present a significant barrier to developing devices using self-organizing materials. To examine the role of peripheral groups in the self-organization of self-assembled multiporphyrinic arrays on surfaces, Pd(II)-linked square and Pt(II)-linked trapezoidal tetrameric porphyrin arrays with peripheral tert-butylphenyl or dodecyloxyphenyl functionalities were investigated using various spectroscopies and atomic force microscopy. The Pd(II) assembled squares disassemble upon deposition on glass surfaces, while the Pt(II) assembled trapezoids are more robust and can be routinely cast on these surfaces. The orientation and length of the peripheral alkyl substituents influence the resultant structures on surfaces. The tert-butylphenyl-substituted porphyrin array forms discrete columnar stacks, which assemble in a vertical direction via pi-stacking interactions among the macrocycles. The tetrameric porphyrin array with dodecyloxyphenyl groups forms a continuous film via van der Waals interactions among the peripheral hydrocarbon chains. The super-molecules with liquid crystal-forming moieties also form three-dimensional crystalline structures at higher deposition concentrations. These observations clearly demonstrate that the number, position, and nature of the peripheral groups and the supramolecular structure and dynamics, as well as the energetics of interactions with the surface, are of key importance to the two-dimensional and three-dimensional self-organization of assemblies such as porphyrin arrays on surfaces.

Nanoscaled materials of organic dyes are of interest for a variety of potential applications because of the rich photonic properties that this class of molecules can impart. One mode to form such nanoscaled materials is via self‐organization and self‐assembly, using reasonably well understood methods in supramolecular chemistry. But there are inherent complexities that arise from the use of organic‐based supramolecular materials, including stability toward dioxygen, structural stability, and nanoarchitectures that may change with environmental conditions. Porphyrinoids have rich photonic properties yet are remarkably stable, have a rigid core, are readily functionalized, and metalation of the macrocycle can impart a plethora of optical, electronic, and magnetic properties. While there are many <10 nm porphyrinic assemblies, which may or may not self‐organize into crystals, there is a paucity of 10–500 nm porphyrinic materials that can be isolated and stored. A variety of strategies towards the latter nanoscopic porphyrinic materials are discussed in terms of design, construction, and nanoarchitecture. The hierarchical structures include colloids, nanorods, nanotubes, nanorings, and nano‐crystalline materials. This prolegomenon emphasizes the supramolecular chemistry, structure‐stability, and structure‐function relationships. The goal herein is to examine general trends and delineate general principles.

Discrete squares and tapes of porphyrins are self-assembled by self-complementary hydrogen bonding between diacetamidopyridyl recognition groups rigidly linked to the chromophore.

Piles of molecules: Self‐assembled nonamer arrays self‐organize into 3D aggregates (see scheme: L=“L‐shaped” porphyrin (corner piece), T=“T‐shaped” porphyrin (side piece), +=“cross‐shaped” porphyrin (center)). The size of the nanoscaled material on surfaces can be controlled from 1 nonamer to 50‐nm‐tall aggregates by chemistry, kinetics, and choice of surface.

No abstract

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.