4. Survey of Novel Multiphoton Active Materials 1257 4.1. Multiphoton Absorbing Systems 1257 4.2. Organic Molecules 1257 4.3. Organic Liquids and Liquid Crystals 1259 4.4. Conjugated Polymers 1259 4.4.1. Polydiacetylenes 1261 4.4.2. Polyphenylenevinylenes (PPVs) 1261 4.4.3. Polythiophenes 1263 4.4.4. Other Conjugated Polymers 1265 4.4.5. Dendrimers 1265 4.4.6. Hyperbranched Polymers 1267 4.5. Fullerenes 1267 4.6. Coordination and Organometallic Compounds 1271 4.6.1. Metal Dithiolenes 1271 4.6.2. Pyridine-Based Multidentate Ligands 1272 4.6.3. Other Transition-Metal Complexes 1273 4.6.4. Lanthanide Complexes 1275 4.6.5. Ferrocene Derivatives 1275 4.6.6. Alkynylruthenium Complexes 1279 4.6.7. Platinum Acetylides 1279 4.7. Porphyrins and Metallophophyrins 1279 4.8. Nanoparticles 1281 4.9. Biomolecules and Derivatives 1282 5. Nonlinear Optical Characterizations of Multiphoton Active Materials 1282

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Role of Structural Factors in the Nonlinear Optical Properties of Phthalocyanines and Related Compounds

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

Supramolecular chemistry, defined as “chemistry outside a molecule”, is at the heart of the development of chemistry of complex systems, molecular devices, ensembles, and nanochemistry.1 This is the chemistry where molecules are able to self-organize, self-assemble, and self-control into systems and the components are often analogues to biological molecules. Metalloporphyrins and metallophthalocyanines are remarkable precursors in supramolecular chemistry, and the rapid development of this chemistry led to assemblies possessing various architectures and properties (photo-, electro-, and catalytic properties and others). Metalloporphyrins are one of the cornerstones on which the existence of life is based, and major biochemical, enzymatic, and photochemical functions depend on the special properties of a tetrapyrrolic macrocycle. However, metalloporphyrins are the only molecules as key elements that require assembly with other elements to form the supramolecular structure, that is, the working device. In natural systems, polypeptides define a given structural organization and hold all the moieties together. Such complex natural devices are not accessible by direct chemical synthesis so far, but their modeling, using simplified designs, has been actively exploited during the last decades. The rapid development of this new area of chemistry has promoted the understanding of the concepts of design and strategies of self-assembly of structures based on intermolecular interactions to result in natural and synthetic supramolecular complexes of metalloporphyrins. Synthetic metalloporphyrin complexes are often used as analogues of natural systems found in photosynthesis, oxygen carriers, and catalysts.2,3 Such research also led to the discovery of new applications of these systems, for example in photodynamic therapy, information storage devices or photoelectrical devices that transform energy in both directions (photocells and lightemitting diodes).4-6 An application of increasing importance is the use of metalloporphyrins as receptors, exploiting their ability to selectively form complexes which can sharply change the spectral properties.7,8 Using molecules that combine different receptor units such as porphyrins and † A.N. Frumkin Institute of Physical Chemistry and Electrochemistry. ‡ Université de Bourgogne. Irina Beletskaya was born in 1933 in Leningrad (USSR). She received her Diploma in 1955, her Ph.D. in 1958, and her Doctor of Chemistry degree in 1963, all at M.V. Lomonosov Moscow State University. The subject for the latter was “Electrophilic Substitution at Saturated Carbon”. She became a Full Professor in 1970. She is currently a head of the Laboratory of Organoelement Compounds at M.V. Lomonosov Moscow State University and a full member (Academician) of Russian Academy of Sciences. She was a recipient of the Lomonosov Prize (1979), the Mendeleev Prize (1982), and the Nesmeyanov Prize (1991). Irina Beletskaya is a chief editor of the Russian Journal of Organic Chemistry. She is the author of more than 1000 articles and a number of monographs. Her current scientific interests are focused on organoelement compounds, transition metal catalysis, and organocatalysis. Chem. Rev. 2009, 109, 1659–1713 1659

Supramolecular chemistry of metalloporphyrins.

Main properties of 5,10,15,20-tetra(4-chlorophenyl)porphyrin in the acetonitrile-perchloric acid system were studied by the method of spectrophotometric titration at standard temperature. The protonation of nitrogen atoms of the tetrapyrrole macrocycle was shown to occur in two steps, through the formation of mono- and diprotonated forms. The corresponding ionization constants and concentration intervals were determined. The diprotonated form of porphyrin was shown to bind effectively iodide, bromide and chloride ions, the stability constants of the complexes of 1:1 and 1:2 composition were determined.

pH-switchable porphyrin receptor for binding halide ions

Spectral Properties of Porphyrins and Their Precursors and Derivatives.

The receptor properties of complexes of 5,10,15,20-tetraphenyl-21,22,23-trimethylporphyrin and 5,10,15,20-tetraphenyl-2,3,7,8,12,13,17,18,21,22,23,24-dodecamethylporphyrin toward hydroxide ion were explored by the method of spectrophotometric titration in methanol with iodine and triflate respectively. We found that in the studied complexes the hydroxide ion is replaced by the respective counterion that leads to a strong response in the visible region of absorption spectrum. The formation constants and the concentration ranges of existence of the complexes were determined.

Cationic tetrapyrrole receptors for selective binding hydroxide ions

The reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with sodium nitrite in trifluoroacetic acid produced 5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrin, 5,15-dinitro-2,3,7,8,12,13,17,18-octaethylporphyrin, and 5,10,15-trinitro-2,3,7,8,12,13,17,18-octaethylporphyrin. Reactions of octaethylporphyrin, mono-, di-, tri-, and tetranitro-substituted porphyrins coordination to cobalt(II) acetate in a chloroform–methanol mixture were studied. The corresponding Co(II) porphyrinates were obtained and identified. It was shown that, upon dissolution of Co(II) octaethylporphyrinates in dimethylformamide in the presence of NaOH, the Co(II)→Co(III) oxidation occurs in the coordination site of the macrocycle.

Synthesis and Spectral Properties of meso -Nitro-Substituted Octaethylporphyrins and Their Co(II) Complexes

[2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato]zinc(II) was synthesized by reaction of [5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato]zinc(II) with N-bromosuccinimide in chloroform–methanol, chloroform–dimethylformamide, and dimethylformamide The reaction of [5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato]zinc(II) with N-chlorosuccinimide in chloroform–methanol or dimethylformamide gave [2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato]zinc(II) [2,3,7,8,12,13,17,18-Octachloro-5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinato]zinc(II) was obtained by chlorination of [5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinato]zinc(II) with excess N-chlorosuccinimide in dimethylformamide The synthesized complexes were identified by electronic absorption spectroscopy, 1H NMR, and mass spectrometry

N. Zh. Mamardashvili

Papers

pH-switchable porphyrin receptor for binding halide ions

Spectral Properties of Porphyrins and Their Precursors and Derivatives.

Cationic tetrapyrrole receptors for selective binding hydroxide ions

Synthesis and Spectral Properties of meso -Nitro-Substituted Octaethylporphyrins and Their Co(II) Complexes

Halogenation of Fluoro-Substituted Zinc(II) Tetraphenylporphyrins at the β-Position