Phthalocyanines (Pcs) and related compounds with their extended two-dimensional pi;-electronic delocalization are important targets to study nonlinear optical responses. The tailorability of these macrocycles allows the fine-tuning of the chemical structure and nonlinear optical response. In this article, the design and main properties of phthalocyanines for second- and third-order nonlinear optical (NLO) and optical limiting applications are discussed, both at the microscopic and macroscopic level. The points of view of synthetic organic chemists and physicists are accorded, the main aim of the review being to highlight the key problems of the field and place them within the general context of NLO materials.

Phthalocyanines and related compounds:organic targets for nonlinear optical applications

Conducting Stacked Metallophthalocyanines and Related Compounds

7.1. Synthesis 306 7.2. Spectroscopic and Redox Properties 307 7.2.1. Optical Spectroscopy 307 7.2.2. Redox Properties 310 7.2.3. Other Characterization Methods 312 8. seco-Porphyrazines 312 8.1. Synthesis 312 8.2. Spectroscopic and Redox Properties 312 8.2.1. Optical Spectroscopy 312 8.2.2. Redox Properties 313 8.2.3. Other Characterization Methods 313 9. Conclusions 313 10. Abbreviations 314 11. Acknowledgments 314 12. References 314

Low Symmetry Phthalocyanines and Their Analogues

Novel boron(III) subphthalocyanines (SubPcs) soluble in organic solvents containing a variety of donor and acceptor substituent groups have been synthesized by boron trihalide-induced cyclotrimerization of adequately substituted derivatives of phthalonitrile in 1-chloronaphthalene. The choice of the substituents on the 1,2-dicyanobenzene derivatives has been made taking into account the high reactivity of the Lewis acid BCl3 toward many functional groups. Considering this limitation, we set out to synthesize phthalodinitriles equipped with iodo, nitro, alkyl- or arylthio, alkyl- or arylsulfonyl groups that are sufficiently stable under the required reaction conditions and also provide an easily accessible set of acceptor/donor substituents. The quadratic and cubic hyperpolarizabilities of these compounds as well as their linear optical and electrochemical properties have been measured by several techniques, including EFISH (at two wavelengths), HRS, and THG, steady-state and time-resolved absorption and f...

Synthesis and Nonlinear Optical, Photophysical, and Electrochemical Properties of Subphthalocyanines

The synthesis, photophysical and photochemical properties of the 4-({3,4,5-tris-[2-(2-ethoxyethoxy)ethyloxy]benzyl}oxy) and 4-({3,4,5-tris-[2-(2-ethoxyethoxy)ethyloxy]benzyl}thio) zinc(II) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen, fluorescence and triplet excited state quantum yields, and triplet state and fluorescence lifetimes of these compounds in dimethylsulfoxide (DMSO). The fluorescence of the complexes was quenched by benzoquinone (BQ). The effects of the substitution on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (6, 7 and 8) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The substituted Zn(II) phthalocyanines showed high triplet and singlet oxygen quantum yields. High singlet oxygen quantum yields are very important for Type II mechanism. Thus, these complexes show potential as Type II photosensitizers.

Synthesis, photophysical and photochemical properties of substituted zinc phthalocyanines

An improved approach to the synthesis of di-disubstituted phthalocyanines from two different phthalyl precursors is described. The method combines substituted 1,3 diiminoisoindoles and 6/7-nitro-1,3,3-trichloroisoindolenine to synthesize phthalocyanine. The method can be applied to the synthesis of hydrogen and metallo phtahlocyanine. The yields are variable, ranging from 17% to 72% depending on the substituents.

Joseph G. Young

Papers

Synthesis and characterization of di-disubstituted phthalocyanines

Synthesis and Characterization of Di-disubstituted Phthalocyanines.