A synthetic approach towards novel octa-substituted zinc(II) phthalocyanines with different solubility and photophysical properties

Abstract

The synthesis and behavior in homogeneous solutions of 2,3,9,10,16,17,23,24-octakis(3-phthalimidopropyloxy)phthalocyaninatozinc(II) (5) and 2,3,9,10,16,17,23,24-octakis(3-aminopropyloxy)phthalocyaninatozinc(II) (6) are reported.

Axially Decorated SiIV‐phthalocyanines Bearing Mannose‐ or Ammonium‐conjugated Siloxanes: Comparative Bacterial Labeling and Photodynamic Inactivation,

“…Phthalocyanines (Pc) are ideal PSs for PDI due to their high 1 O 2 quantum yields ( Φ Δ ), their stability toward self‐oxidation and their ability to absorb light in the near‐infrared region but also tend to aggregate in aqueous media owing to their high hydrophobicity. The tendency of Pcs toward aggregation is an intrinsic characteristic that needs to be addressed to maximize their efficiency . Multiple approaches have been undertaken to overcome their poor water solubility, such as the introduction of sixteen polyoxyethylene side chains , the attachment of four and eight D‐galactose units to a Zn II Pc , the use of a tetra‐substituted cationic Zn II Pc for in vitro photodynamic therapy (PDT) , the attachment to a Pc of sixteen quaternized imidazolyl moieties for PDT in vitro , the synthesis of Pcs functionalized with glucose and lactose , and glycerol substitution of Pcs .…”

“…Kenney and Oleinick have successfully established axially siloxane‐functionalized Si IV Pcs, which eventually led to the U.S. Food and Drug Administration (FDA)‐approved PDT drug Pc4 for the treatment of prostate and metastatic cutaneous cancers . Some examples of functionalized Si IV Pcs demonstrate the versatility of axial decoration, as they have been used for PDT of cancer , for PDI of fungi and for PDI of bacteria .…”

Synthesis of 2,3,9,10,16,17,23,24-Octasubstituted Phthalocyaninatozinc(II) Complexes Mediated by Reductive Agents

“…2 Because phthalocyanines are barely soluble, considerable efforts have been made to prepare lipophilic derivatives by the introduction of peripheral alkyl chains. 3 Most octasubstituted phthalocyanines are symmetrical compounds and contain two substituents on each of the benzene rings. 1a As single symmetrical compounds, octasubstituted phthalocyanines are generally less soluble in organic solvents than are the corresponding tetrasubstituted phthalocyanines.…”

“…1a Because synthesis of octasubstituted zinc(II) phthalocyanines that have four identical substituents in the 2-, 9-, 16-, and 23-positions, and a different group of identical substituents at the 3-, 10-, 17-, and 24-positions affords a mixture of positional isomers, these compounds could be expected to have a greater solubility than those with eight identical substituents. However, 2, 3,9,10,16,17,23,24-octasubstituted phthalocyanines prepared from phthalonitriles with two different substituents in the 4-and 5-positions have received relatively little study, and only few derivatives have been reported. 4 Similar metallophthalocyanines octasubstituted in the 1-, 3-, 8-, 10-, 15-, 17-, 22-, and 24-positions have, however, been described more extensively in the literature.…”

“…6 To improve the amphiphilicity of these compounds, we incorporated substituents derived from the (dibutylamino)methyl group, instead of a phthalimidomethyl or aminomethyl group, in the peri-pheral positions of the phthalocyanines. We report the synthesis and spectroscopic properties of three novel 2, 3,9,10,16,17,23, complexes that are highly soluble in polar organic solvents.…”