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In this work tetrakis–[(thiopheneethoxy) phthalocyaninato] zinc(II) (1), tetrakis–[(thiopheneethoxy) phthalocyaninato] indium (II) chloride (2), tetrakis [(benzo [d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (3), and tetrakis [(benzo [d]thiazol-2-yl phenoxy)phthalocyaninato] indium (II) chloride (4) were linked to both gold nanospheres (AuNSs) and gold nanotriangles (AuNTs) via Au-S and Au-N (the latter for complexes 3 and 4 only) self assembly. The photophysicochemical behaviour of complexes and their conjugates were studied. The conjugates yielded improved triplet and singlet quantum yields, with nanospheres displaying better properties than nanotriangles. The conjugates with a benzothiazole phenoxy substituent also yielded better properties than their thiophene ethoxy counterpart. These conjugates especially those with a benzothiazole phenoxy substituent have potential as photosensitisers for photodynamic therapy applications.

Glutathione (GSH) capped Au nanotriangles (AuNTs–GSH) and nanospheres (AuNSs–GSH) are covalently linked to symmetric Zn phthalocyanine (ZnPc) substituted with phenoxy propanoic acid substituents only (complex 1) and two asymmetric ZnPc, each containing one phenoxy propanoic acid and three benzothiazole phenoxy moieties (complex 2), and one phenoxy propanoic acid and no other ligands (complex 3). The photophysicochemical behaviour of Pc complexes and their conjugates were studied. All conjugates displayed improved triplet and singlet oxygen quantum yields with decreases in fluorescence quantum yields compared to their respective Pc complexes. The conjugates of asymmetric complexes 2 and 3, afforded much higher triplet and singlet oxygen quantum yields compared to the symmetric complex 1, and could serve as good candidates for photodynamic therapy.

The syntheses of neodymium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (2), bis europium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (3), bis dysprosium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (4) and their conjugated analogues with nitrogen doped quantum dots (NGQDs) are reported herein. The optical nonlinearity of the sandwich-type phthalocyanine complexes and their conjugates with NGQDs were studied in dimethyl sulfoxide using the open aperture Z-scan technique at an excitation wavelength of 532 nm with a 10 ns pulse. The nonlinear absorption coefficient (βeff) value of the samples ranges from 15 cm GW−1 to 89.6 cm GW−1. Complex 4 and its conjugates afforded a strong optical limiting behaviour compared to the other samples. These fabricated complexes and their conjugates with NGQDs could serve as a plausible nonlinear optical (NLO) material due to their fascinating NLO properties.

The synthesis of a novel asymmetric phthalocyanine, (4-(4-(benzo[d]thiazol-2-yl)phenoxy)-2,10,17-tris(4-(2-carboxyethyl)phenoxy)phthalocyaninatol)zinc(II), complex 3, is reported. Complex 3 together with the previously reported complexes tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (4) and 3-(4-((3,17,23-tris(4-(benzo[d]thiazol-2-yl)phenoxy)phthalocyaninatol)oxy)phenyl)propanoic acid zinc(II) (5), were linked to gold nanotriangles (AuNTs) through S–Au/Au–N self-assembly to afford the conjugates (3-AuNTs, 4-AuNTs and 5-AuNTs). The photophysicochemical behaviour of the complexes and their conjugates were studied. The asymmetric complexes 3 and 5, displayed improved triplet and singlet oxygen quantum yields compared to the symmetric complex 4, while all conjugates displayed improved triplet and singlet oxygen quantum yields compared to their respective complexes alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.

Novel zinc(II) 3-(4-((3,17,23-tris(4-(benzo[d]thiazol-2-yl)phenoxy)phthalocyanine-9-yl)oxy)phenyl)propanoic acid (complex 3) was synthesised. Complex 3 was subsequently reacted with gold nanoparticles (AuNPs), chitosan (CT) and a gold–chitosan (AuCT) hybrid to form 3-AuNPs, 3-CT and 3-AuCT, respectively. The conjugates afforded a decrease in fluorescence quantum yield with a corresponding increase in the triplet and singlet quantum yields compared to complex 3. The in vitro dark cytotoxicity and photodynamic therapy activity (PDT) of complex 3 and 3-AuCT composites were investigated against epithelial breast cancer cells (MCF-7) with both the samples showing minimum dark cytotoxicity. They both accounted for a cell viability of ≥90% at a concentration of ≤59.2 μg mL−1. 3-AuCT showed better PDT activity (compared to 3 alone) with less than 50% viable cells at a concentration of ≥29.6 μg mL−1 making it potentially applicable for PDT. On the other hand, AuCT displayed some activity against cancer cells, probably due to photothermal activity since gold is a light absorber, however it had more than 50% viable cells at a concentration of ≤59.2 μg mL−1.

The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] ( 2 ) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine ( 3 ) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag 3 Au 1 NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2 –AgNPs–GSH, 3 –AgNPs–GSH, 2 –AuNPs–GSH, 3 –AuNPs–GSH, 2 -Ag 3 Au 1 NPs–GSH and 3 -Ag 3 Au 1 NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.

This work reports on the covalent linkage of (3-aminopropyl)triethoxysilane (APTES) functionalised iron oxide (IONPs–APTES) and silica (SiNPs–APTES) nanoparticles with zinc(II) tetra–([3–(4–phenoxy) propanoic acid) phthalocyanine] (1) and zinc(II) mono–([3–(4–phenoxy) propanoic acid) phthalocyanine (2) via an amide bond to form the conjugates, 1–IONPs-APTES, 1–SiNPs–APTES, 2-IONPs-APTES and 2-SiNPs-APTES). The photophysicochemical behaviour of the conjugates was investigated. These were characterized by a decrease in the fluorescence quantum yields and lifetimes, and an increase in the triplet quantum yield and singlet oxygen quantum yield when compared to complex 1 and 2 alone. The conjugates to IONPs-APTES displayed higher ΦT than those of SiNPs-APTES probably due to the heavy atom effect of iron compared to silica and the high loading capacity of the relatively smaller iron oxide NPs, however, there was no significant difference in the ΦΔ values of 2-IONPs-APTES (ΦΔ=0.59) and 2-SiNPs-APTES (ΦΔ=0.58), suggesting that the energy transfer process between the excited triplet state of 2-IONPs-APTES and ground state molecular oxygen was not effective. Photodynamic antimicrobial chemotherapy (PACT) studies showed that linkage of Pcs to NPs improves their photoinactivation capability against Staphylococcus aureus and Escherichia coli. IONPs-APTES and its conjugates generally displayed the highest log reductions than SiNPs-APTES and its conjugates except for studies after 75 min of irradiation for S. Aureus where the log reductions are the same. 2-IONP-APTES was recovered using a magnet after each photodegradation cycle and its stability after 3 cycles confirmed re-usability.

The syntheses of two zinc(II) phthalocyanines (ZnPcs) having either imidazole (ZnPc 1) or pyridiloxy (ZnPc 2) moieties as their macrocycle substituents are reported. Quaternization of the ZnPcs with methyl iodide afforded water soluble cationic phthalocyanines. The photophysical, photochemical properties and photodynamic therapy (PDT) activity of the ZnPcs were studied in solution. The fluorescence quantum yield and lifetime of ZnPc 1 were higher as compared to ZnPc 2. ZnPc 2 afforded higher triplet state (ΦT) and singlet oxygen quantum yields (ΦΔ) in comparison to ZnPc 1. The PDT activity of ZnPcs was investigated against human breast adenocarcinoma cells (MCF–7). The two compounds afforded a very minimal in vitro dark cytotoxicity with 85% viable cells at concentration ≤80 μM. On irradiation of the cells having the ZnPcs, ≥50% cell death was recorded for ZnPc 1 which was also evidenced by the cells photo–micrograph.

In this work, we report on the synthesis of tris-[(2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-5-yl)methoxy)-2-(4-benzo[d]thiazol-2-ylphenoxyphthalocyaninato] zinc(II) (complex 3) and its linkage to gold nanoparticles (AuNPs) of different shapes through S-Au/N-Au self-assembly. The conjugates of complex 3 (with both gold nanorods (AuNR) and nanospheres (AuNS)), displayed decreased fluorescence quantum yield with corresponding improved triplet and singlet quantum yields compared to complex 3 alone, however 3-AuNR showed improved properties than 3-AuNS. Complex 3 showed relatively low in vitro dark cytotoxicity against the epithelial breast cancer cells with cell survival ≥ 85% at concentration ≤ 160 μg/mL but afforded reduced photodynamic therapy activity which may be due to aggregation. 3-AuNR afforded superior PDT activity with50% viable cells at concentration ≥ 40 μg/mL in comparison to 3-AuNS with50% viable cells at concentration ≥ 80 μg/mL. The superior activity of 3-AuNR is attributed to the photothermal therapy effect since nanorods absorb more light at 680 nm than nanospheres.