title: Synthesis, supramolecular behavior, and in vitro photodynamic activities of novel zinc(II) phthalocyanines "side-strapped" with crown ether bridges.
abstract: Two new tetra- or di-α-substituted zinc(II) phthalocyanines 5 and 6 have been prepared through a "side-strapped" method. In the molecules, the adjacent benzene rings of the phthalocyanine core are linked at α-position through a triethylene glycol bridge to form a hybrid aza-/oxa-crown ether. The tetra-α-substituted phthalocyanine 5 shows an eclipsed self-assembly property in CH2Cl2 and the effect on the di-α-substituted analogue 6 is significantly weakened. Furthermore, the crown ethers of these compounds can selectively complex with Fe(3+) or Cu(2+) ion in DMF, leading to formation of J-aggregated nano-assemblies, which can be disaggregated in the presence of some organic or inorganic ligands, such as triethylamine, tetramethylethylenediamine, CH3COO(-), or OH(-). In addition, both compounds are efficient singlet oxygen generators with the singlet oxygen quantum yields (Φ(Δ)) of 0.54-0.74 in DMF relative to unsubstituted zinc(II) phthalocyanine (Φ(Δ)=0.56). They exhibit photodynamic activities toward HepG2 human hepatocarcinoma cells, but the compound 6, which has more than 40-fold lower IC50 value (0.08 μM) compared to the analogue 5 (IC50=3.31 μM), shows remarkablely higher in vitro photocytotoxicity due to its significantly higher cellular uptake and singlet oxygen generation efficiency. The results suggest that these compounds can serve as promising multifunctional materials both in (opto)electronic field and photodynamic therapy.
authors.affiliation: College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou (P. R. China), Fax: (+86) 591-22866227.
authors.forename: Xing-Wei
authors.initials: XW
authors.lastname: Chen
authors.forename: Mei-Rong
authors.initials: MR
authors.lastname: Ke
authors.forename: Xing-Shu
authors.initials: XS
authors.lastname: Li
authors.forename: Wen-Liang
authors.initials: WL
authors.lastname: Lan
authors.forename: Miao-Fen
authors.initials: MF
authors.lastname: Zhang
authors.forename: Jian-Dong
authors.initials: JD
authors.lastname: Huang
mesh_terms: D043844:Crown Ethers / Q000737:chemistry*; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D054833:Isoindoles; D046911:Macromolecular Substances / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D017319:Photosensitizing Agents / Q000138:chemical synthesis* / Q000737:chemistry; D017967:Zinc Compounds
chemical_list: D043844:Crown Ethers; D007211:Indoles; D054833:Isoindoles; D046911:Macromolecular Substances; D009942:Organometallic Compounds; D017319:Photosensitizing Agents; D017967:Zinc Compounds; C052159:Zn(II)-phthalocyanine
keywords: J aggregation; crown compounds; metal ions; photodynamic therapy; phthalocyanines