Department of Pharmaceutical Chemistry and Drug Control, Faculty of Pharmacy in Hradec Kralove, Charles University in Prague, Heyrovskeho 1203, 50005, Hradec Kralove, Czech Republic.
Inorg Chem. 2012 Apr 2;51(7):4215-23. doi: 10.1021/ic2027016. Epub 2012 Mar 12.
Magnesium(II), zinc(II), and metal-free phthalocyanines (Pcs) and azaphthalocyanines (AzaPcs) containing alkylsulfanyl, aryloxy, and dialkylamino peripheral substituents have been synthesized. The complexation of magnesium(II) by metal-free Pcs and AzaPcs has been studied in detail to determine the optimal reaction conditions necessary to ensure a complete conversion. Photophysical and photochemical measurements in tetrahydrofuran showed that magnesium(II) AzaPcs with aryloxy and alkylsulfanyl substituents have excellent fluorescent properties (Φ(F) up to 0.73) and that the corresponding zinc(II) Pcs are efficient singlet oxygen producers (Φ(Δ) up to 0.68). The presence of dialkylamino substituents causes intramolecular charge transfer within the molecule that competes with fluorescence and singlet oxygen formation. Alkylsulfanyl MgAzaPc and ZnAzaPc were the most photostable compounds among the series of studied derivatives. In addition, high molar absorption coefficients (ε ∼ 300,000 M(-1) cm(-1)), absorption (λ(max) ∼ 650 nm), and emission (λ(em) ∼ 660 nm, high Φ(F)) in the red region suggest that these molecules are potential fluorescent probes that are superior to the commercial red cyanine dye Cy5. MgAzaPc, when incorporated into lipidic bilayers of liposomes, maintains excellent fluorescence properties (Φ(F) = 0.64). Water-soluble MgAzaPc with quaternary ammonium peripheral substituents retained a high fluorescence quantum yield even in water (Φ(F) = 0.25). The described properties show that magnesium(II) AzaPcs are excellent red-emitting fluorophores with potential applications as fluorescent probes in sensing or in vitro imaging applications.
镁（II），锌（II）和无金属酞菁（Pc）和氮杂酞菁（AzaPc）含有烷基硫烷基，芳氧基和二烷基氨基外围取代基已被合成。详细研究了无金属 Pc 和 AzaPc 与镁（II）的络合，以确定确保完全转化所需的最佳反应条件。在四氢呋喃中的光物理和光化学测量表明，具有芳氧基和烷基硫烷基取代基的镁（II）AzaPc 具有极好的荧光性质（Φ（F）高达 0.73），而相应的锌（II）Pc 是有效的单重态氧产生剂（Φ（Δ）高达 0.68）。二烷基氨基取代基的存在会导致分子内电荷转移，与荧光和单重态氧形成竞争。烷基硫烷基 MgAzaPc 和 ZnAzaPc 是所研究衍生物系列中最光稳定的化合物。此外，高摩尔吸光系数（ε∼300,000 M（-1）cm（-1）），吸收（λ（max）∼650nm）和发射（λ（em）∼660nm，高Φ（F））在红色区域表明这些分子是潜在的荧光探针，优于商业红色氰基染料 Cy5。当 MgAzaPc 掺入脂质双层的脂质体中时，保持极好的荧光性质（Φ（F）= 0.64）。带有季铵盐外围取代基的水溶性 MgAzaPc 即使在水中也保持高荧光量子产率（Φ（F）= 0.25）。所述性质表明，镁（II）AzaPc 是极好的红色发射荧光团，具有作为荧光探针在传感或体外成像应用中的潜在应用。
