Abimbola Ogunsipe

Photophysical and photochemical studies of zinc(II) phthalocyanine derivatives—effects of substituents and solvents

The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II) phthalocyanines are reported. The complexes studied are zinc phthalocyanine (ZnPc), zinc tetra(tert-butylphenoxy)phthalocyanine [ZnPc(TBPh)4], zinc octa(methylphenoxy)phthalocyanine [ZnPc(MPh)8], zinc tetranitrophthalocyanine [ZnPc(NO2)4], zinc octachlorophthalocyanine (ZnPcCl8), zinc tetrasulfophthalocyanine [ZnPc(SO3−)4], a mixture of zinc mono-, di-, tri- and tetrasulfophthalocyanine [ZnPc(SO3−)mix] and zinc naphthalocyanine (ZnNPc). It was found that the presence of peripheral substituents on the macrocycle enhances the yield of the triplet state. Among the different substituents, the sulfonated derivative, ZnPc(SO3−)mix, has the longest triplet lifetime (τT) and the highest singlet oxygen quantum yield (ϕΔ). The near infra-red absorptions of the solvents reveal that solvents that absorb around 1100 nm (triplet energy level) and around 1270 nm (singlet oxygen energy level), quench the triplet state of the ZnPc derivative as well as singlet oxygen. Although water has a high singlet oxygen quenching effect, the ϕΔ value for ZnPc(SO3−)mix in water is still reasonably high at 0.48, which may provide an explanation for the efficient photosensitization by this molecule in photodynamic studies.

Solvent effects on the photochemical and fluorescence properties of zinc phthalocyanine derivatives

The effects of solvents on the singlet oxygen, photobleaching and fluorescence quantum yields for zinc phthalocyanine (ZnPc) and its derivatives; (pyridino)zinc phthalocyanine ((py)ZnPc), zinc octaphenoxyphthalocyanine (ZnOPPc) and zinc octaestronephthalocyanine (ZnOEPc), is presented. The effects of the solvents on the ground state spectra are also discussed. The largest red shift of the Q band was observed in aromatic solvents, the highest shift being observed for 1-chloronaphthalene. Higher singlet fluorescence quantum yields were observed in THF for ZnPc and ZnOPPC. Also in the same solvent phototransformation rather than photobleaching was observed for ZnOPPc. Split Q band in the emission and excitation spectra of ZnOPPc was observed in some solvents and this is explained in terms of the lowering of symmetry following excitation.

Photophysicochemical consequences of bovine serum albumin binding to non-transition metal phthalocyanine sulfonates.

The interactions between bovine serum albumin (BSA) and sulfonated metallophthalocyanine (MPc) complexes of aluminum (AlPcS(mix)), zinc (ZnPcS(mix)), silicon (SiPcS(mix)), germanium (GePcS(mix)) and tin (SnPcS(mix)) are studied using fluorescence quenching of BSA by MPc complexes. The fluorescence quantum yields of the non-aggregated MPc complexes (AlPcS(mix), GePcS(mix) and SiPcS(mix)) decreased in the presence of BSA, but increased for the aggregated ZnPcS(mix) and SnPcS(mix) complexes. The BSA: MPc conjugates were less stable than the corresponding MPc complexes. The quenching constants were much higher for the non-aggregated complexes. The aggregated nature of the complexes also affected the rate constants (k(F), k(IC), k(ISC)) for the deactivation of the excited singlet state.

Effects of central metal on the photophysical and photochemical properties of non-transition metal sulfophthalocyanine

The photophysical and photochemical properties and quenching (by 1,4-benzoquinone) of metallophthalocyanine sulfonates of aluminium (AlPcSmix), zinc (ZnPcSmix), silicon (SiPcSmix), germanium (GePcSmix) and tin (SnPcSmix) are presented. The quantum yield values of fluorescence (ΦF), triplet state (ΦT), singlet oxygen (ΦΔ) and photodegradation (Φd) were determined and the observed trends in their variation among the complexes discussed in terms of aggregation and the heavy atom effect. 1,4-benzoquinone effectively quenched the fluorescence of the complexes. Quenching analyses gave positive deviations from Stern-Volmer behavior, suggesting the existence of static quenching in addition to dynamic quenching. The static and dynamic components of the quenching were separated using a modified Stern-Volmer equation and the “sphere of action quenching model”. The quenching constant was found to be a function of the radius of the central metal ion.

Influence of cyclodextrins on the fluorescence, photostability and singlet oxygen quantum yields of zinc phthalocyanine and naphthalocyanine complexes

The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Jobs plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.

Syntheses and photophysics of new phthalocyanine derivatives of zinc, cadmium and mercury

The syntheses of novel tetra{2,(3)-pyridyloxyphthalocyaninato} complexes of zinc, cadmium and mercury (TPyZnPc, TPyCdPc and TPyHgPc) are presented. Their spectral and photophysical properties (as well as those of their unsubstituted counterparts: ZnPc, CdPc and HgPc) are investigated. TPyZnPc and TPyCdPc are aggregated in non-coordinating solvents such as chloroform, while TPyHgPc is demetallated, as evident from their respective absorption spectra. The trends in fluorescence (ΦF), triplet (ΦT) and singlet oxygen (ΦΔ) quantum yields are explained in terms of relative strengths of spin–orbit coupling induced by the respective central metal ions in the complexes. The effect of the pyridyloxy substituents is a decrease in ΦF and an increase in ΦT values. The complexes are less fluorescent in DMSO but possess higher ΦT, triplet lifetimes (τT) and ΦΔ therein.

Microwave synthesis and photophysics of new tetrasulfonated tin(II) macrocycles

This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (<1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.

Synthesis and photophysical properties of a covalently linked porphyrin-phthalocyanine conjugate

The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.

Photophysical, photochemical and bovine serum albumin binding studies on water-soluble gallium(III) phthalocyanine derivatives

Spectral, photophysical, photochemical and bovine serum albumin binding studies on some gallium(III) derivatives - {1,(4)-(tetrapyridyloxyphthalocyaninato)gallium(III), (αGaPc); 2,(3)-(tetrapyridyloxyphthalocyaninato)gallium(III), (βGaPc); and their quaternized derivatives: QαGaPc and QβGaPc)} are hereby presented. β-Substituted complexes are more fluorescent, but show lower tendencies to undergo intersystem crossing than the α-substituted, as judged by their fluorescence and triplet quantum yield values. The quaternized derivatives (QGaPc) are water-soluble and non-aggregated, which makes them potential photosensitizers of choice for photodynamic therapy applications; these amphiphilic compounds also bind strongly to bovine serum albumin in 1:1 stoichiometries, and with binding constants (Kb) in the order of 106 M−1.

Protonation of some non-transition metal phthalocyanines — spectral and photophysicochemical consequences

The photophysics and photochemistry of phthalocyanine complexes of magnesium (MgPc), aluminum chloride (ClAlPc) and zinc (ZnPc) are studied in N,N′-dimethylformamide (DMF). The values obtained for the photophysical and photochemical parameters are normal for simple metallophthalocyanine (MPc) complexes. Protonation of the azomethine bridges reduced the photoactivities of the complexes considerably; however the excited triplet states of the protonated species are more stable towards ground state oxygen. The interaction of the non-protonated MPcs with ground state oxygen is shown to be diffusion-assisted, with bimolecular rate constant values of the order of 1010 M-1.s-1. MgPc could not be protonated; it was easily demetalated by the protonating acid. The kinetics of the demetalation yielded the rate equation: Rate = 0.1[MgPc][H+]2/3