Porphyrins and phthalocyanines have outstanding chemical and thermal stability. The macrocyclic structure and chemical reactivity of tetrapyrroles offers architectural flexibility and facilitates the tailoring of chemical, physical and optoelectronic parameters. The specific optical properties of the tetrapyrrole macrocycle combined with the synthetic methodologies now available and the already available theoretical and spectroscopic knowledge on their optical behavior make porphyrins a target of choice for this area. They are versatile organic nanomaterials with a rich photochemistry and their excited state properties are easily modulated through conformational design, molecular symmetry, metal complexation, orientation and strength of the molecular dipole moment, size and degree of conjugation of the π-systems, and appropriate donor-acceptor substituents. Here we review the structural chemistry and optical properties of recently synthesized porphyrin derivatives that offer potential for nonlinear optical (NLO) applications and complement existing studies on phthalocyanines. Classes of interest include the classic A4 symmetric tetrapyrroles, while optimized systems include push-pull porphyrins, oligomeric and supramolecular self-assembled systems, films and nanoparticle systems, and highly conjugated porphyrin arrays.

Nonlinear Optical Properties of Porphyrins

The self-assembly and self-organization of porphyrins and related macrocycles enables the bottom-up fabrication of photonic materials for fundamental studies of the photophysics of these materials and for diverse applications. This rapidly developing field encompasses a broad range of disciplines including molecular design and synthesis, materials formation and characterization, and the design and evaluation of devices. Since the self-assembly of porphyrins by electrostatic interactions in the late 1980s to the present, there has been an ever increasing degree of sophistication in the design of porphyrins that self-assemble into discrete arrays or self-organize into polymeric systems. These strategies exploit ionic interactions, hydrogen bonding, coordination chemistry, and dispersion forces to form supramolecular systems with varying degrees of hierarchical order. This review concentrates on the methods to form supramolecular porphyrinic systems by intermolecular interactions other than coordination chemistry, the characterization and properties of these photonic materials, and the prospects for using these in devices. The review is heuristically organized by the predominant intermolecular interactions used and emphasizes how the organization affects properties and potential performance in devices.

Self-Organized Porphyrinic Materials

There is currently an intensive effort to develop methods for producing materials with two-dimensionally (2D) or threedimensionally (3D) structured patterns and arrays, which are of great importance and interest because of their potential applications in the development of optoelectronic and microelectronic devices, [ 1–4 ] and the fabrication of chemical and biological sensors. [ 5 , 6 ] In the most recent developments, the fabrication of 2D or 3D structured patterns and arrays via colloidal self-assembly is particularly attractive. [ 7–15 ] In addition to being inexpensive, this method offers relative ease of processing and requires short processing time, compared to the stepwise manner of microfabrication techniques. [ 16–20 ] Typical building blocks of these self-assembly are polystyrene (PS) or poly(methyl methacrylate) (PMMA) latex spheres, poly(dimethyl siloxane) (PDMS), silica spheres, emulsion droplets with narrow size distribution. [ 9 , 21–23 ]

Ordered Nanosphere Alignment of Porphyrin for the Improvement of Nonlinear Optical Properties

The self-assembed chitosan CdSe quantum dots (QDs) and chitosan CdSe−ZnS core−shell QDs films have been prepared by using layer-by-layer electrostatic technique. The well-ordered nanostructure and the layer-by-layer deposition of the QDs are revealed by AFM and exciton absorption spectra, respectively. The optical nonlinearity of the composite films were studied by using Z-scan technique with femtosecond pulses at the wavelength of 790 nm, the value of third-order susceptibility of core−shell QDs are measured to be about 1.1 × 10-8 esu, which is about 200% larger than that of CdSe QDs of 5.3 × 10-9 esu. This has potential applications in all-optical switches in optical information processing.

Preparation and third-order optical nonlinearity of self-assembled chitosan/CdSe-ZnS core-shell quantum dots multilayer films.

The preparation and characterization of a self-assembled material showing a high nonlinear response and good photostability to ultrashort laser pulses is presented. The material is built by alternate deposition of tetrakis(4-sulfonatophenyl)porphyrin diacid (H4TPPS2−) and poly(diallyldimethylammonium chloride) (PDDA) forming electrostatically self-assembled multilayers (ESAMs). UV-visible absorption and emission experiments show that in this matrix H4TPPS2− is present mainly in its J-aggregated form. Furthermore, linear dichroism experiments on a 3 bilayer film show a preferential alignment of the porphyrin aggregate with the J-band transition dipole moment parallel to the film surface. The two photon absorption (TPA) properties of these films are investigated with the Z-scan technique at 806 nm, employing 130 fs pulses. The samples exhibit strong nonlinearities with a very large two-photon absorption coefficient βTPA of 50 cm GW−1. The origin of this large response is investigated. It has been already demonstrated that aggregation enhances the molecular TPA cross section of H4TPPS2− from 30 to 1000 GM in water solution thanks to cooperative effects. In a 20 bilayer film a further increase by a factor of 1.7 is observed and explained in terms of preferential alignment of J-aggregates in the multilayers.

Large third-order nonlinear optical response of porphyrin J-aggregates oriented in self-assembled thin films{

An ultrathin nanoscopic multilayer film has been fabricated through the electrostatic layer-by-layer self-assembly of negatively charged 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin (DHP) and oppositely charged polyethylenimine (PEI). UV−vis spectra showed a continuous and uniform deposition process of PEI and DHP. The film structure was characterized by small-angle X-ray diffraction measurement and AFM images. The nonlinear optical properties of ultrathin film were studied by Z-scan technique with laser duration of 8 ns at a wavelength of 532 nm. The film sample exhibited strong nonlinear saturated absorption and a self-defocusing effect. The nonlinear absorption coefficient and refractive index of the self-assembly ultrathin film are −9.7 × 10-5 m/W and −7.56 × 10-12 m2/W, respectively.

Third-order nonlinear optical properties of an ultrathin film containing a porphyrin derivative.

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Third-order nonlinear optical properties of an ultrathin film containing a porphyrin derivative.