Phthalocyanine and naphthalocyanine

Ring systems intermediate between phthalocyanines and naphthalocyanines are known 263,264 (51) is such a compound. They are most simply called benzonaphthoporphyrazines, and various zinc(II) complexes with cationic (A--m e t hy 1 pyridini um-3-oxy) substituents have Amax in the range 680-750 nm in solution or in Cremophor micelles, and show promise in bioassays in vivo.264... 

Most activity here has been with the phthalocyanine and naphthalocyanine complexes. 

The phthalocyanines, naphthalocyanines, and certain of their metal derivatives (Figure 6.17) are infrared fluorophores. 61"64 As a class, they are exceptionally stable compounds, with copper (Cu) phthalocyanine (not a fluorophore) remaining intact above 300 °C in air. First used for textile dyeing in the last century and still widely used, there is a rich chemistry of phthalocyanines. Most derivatives can be made by prolonged heating of a phthalimide or phthalic acid derivative with a metal in powder or salt form at elevated temperature. Several derivatives absorb in the near-IR, and either fluoresce or phosphoresce. The electronic transitions of phthalocyanines are complex and have been extensively studied, at least in part because the symmetry of the molecule makes theoretical calculations of its spectroscopic behavior more tractable. Unsubstituted phthalocyanines and naphthalocyanines are, as a class, very insoluble in solvents other than, for instance, nitrobenzene. Sulfonated phthalocyanines are water soluble and exhibit spectra comparable to the parent derivative. Photolumines-cent phthalocyanines (Pcs) include SiPc, ZnPc, and PC itself. These compounds have been little used for practical infrared fluorometry to date however, Diatron Corpora-... 

The present article reviews the photochemical deactivation modes and properties of electronically excited metallotetrapyrroles. Of the wide variety of complexes possessing a tetrapyrrole ligand and their highly structured systems, the subject of this survey is mainly synthetic complexes of porphyrins, chlorins, corrins, phthalocyanines, and naphthalocyanines. All known types of photochemical reactions of excited metallotetrapyrroles are classified. As criteria for the classification, both the nature of the primary photochemical step and the net overall chemical change, are taken. Each of the classes is exemplified by several recent results, and discussed. The data on exciplex and excimer formation processes involving excited metallotetrapyrroles are included. Various branches of practical utilization of the photochemical and photophysical properties of tetrapyrrole complexes are shown. Motives for further development and perspectives in photochemistry of metallotetrapyrroles are evaluated. 

At the first stage of the research, several zinc(II) tetrapyrroles (porphyrin, phthalocyanine and naphthalocyanine derivatives) were investigated [27] in the systems containing sacrificed compounds. The results obtained contributed to the development of the theory of redox reactions and energy-transfer processes, they were, however, of little practical significance. 

Approaches to the formation of condensed isoindolones 05COC1261. Axially modified gallium phthalocyanines and naphthalocyanines for optical limiting 05CSR517. 

Synthesis, properties, and applications of ruthenium phthalocyanine and naphthalocyanine complexes 07CCR1128. 

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes 06CCR(250)424. 

Covalent/covalent bonds in p-oxo-bridged polymers [PcM(IV)0] (Pc = phthalocyanine) (Fig. 7-20) with tetravalent Si, Ge or Sn have been obtained by polycondensation of dihydroxy-metal macrocycles such as the porphyrins, phthalocyanines and naphthalocyanines (M = Si(OH)2, Ge(OH)2, Sn(OH)2) in a high boiling solvent (the HO groups can be activated by better leaving groups such as CF3COO or under catalysis by FeCh) or in the solid state (under... 

Phthalocyanine and naphthalocyanine are guest dye dopants suitable for the near infrared (IR) region. PVK is used as usual, as the hole transport polymer, Alqs, or a sulforamide derivative (Al(qs)3) is used as the host dye. The absorbance spectra of the guest dyes are significantly different from the emission spectra of the host dyes. However, the high molar absorption of the host dye dopants result in such efficiencies of energy transfer that are comparable to quinacridone or rubrene dopants. 

Hitmen, C., F. Coowar, and M. Savy (1989). Oxygen reduction in acid media Investigations by electroreflectance on adsorbed iron phthalocyanine and naphthalocyanine layers. J. Electroanal. Chem. 264,167-180. 

At least one of the ring in and out of plane deformations is clearly observed in colloidal silver at about 680 cm" This frequency has been assigned to a macrocycle breathing in phthalocyanines and naphthalocyanines most of assignments in aromatic systems propose this band to an out of plane CH or ring deformations ... 

Unsymmetrically substituted water-soluble phthalocyanines and naphthalocyanines as well as water-soluble tetrasubstituted phthalocyanines [R4PCM, R = COOH, SO3H M = Zn, A1(0] have been applied in photodynamic cancer therapy [109]. 

Flora WH, Hall HK, Armstrong NR (2002) Guest emission processes in doped organic light-emitting diodes use of phthalocyanine and naphthalocyanine near-IR dopants. J Phys Chem B 107 1142-1150... 

Jiang JZ, Bao M, Rintoul E, Arnold DP (2006) Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes. Coord Chem Rev 250(3 ) 424 148... 

TABLE 15.6 Preparation of Precursors and Their Conversion to Phthalocyanine and Naphthalocyanine... 

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