Aggregation of gold(<scp>i</scp>) complexes: phosphorescence <i>vs.</i> singlet oxygen production

Pinto, Andrea; Ward, Jas S.; Smith, Martin B.; Rodríguez, L.

doi:10.1039/d2dt01154a

Cited by 6 publications

(10 citation statements)

References 49 publications

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“…To quantify this process, the standard reference 1 H -phenal-1-one was used (Figure S23). The singlet oxygen quantum yield production values (45–92%; Table ) obtained are significantly higher compared with other gold(I) complexes found in the literature. ,− …”

Section: Resultssupporting

confidence: 58%

Ligand and Gold(I) Fluorescein–AIEgens as Photosensitizers in Solution and Doped Polymers

et al. 2023

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The synthesis of fluorescein propargyl diether (L) and two different dinuclear gold(I) derivatives containing a water-soluble phosphane [1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane (PTA) for complex 1 and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) for complex 2] has been successfully performed. All compounds display intrinsic emission from fluorescein, being less intense for gold(I) complexes due to the heavy-atom effect. All compounds aggregate in acetonitrile/water mixtures with the formation of larger aggregates for those samples containing more water content, as evidenced by dynamic light scattering and small-angle X-ray scattering experiments, in agreement with the absorption and emission data. The emission of the samples increases when they are used to obtain luminescent materials with four different organic matrices [poly(methyl methacrylate, polystyrene (PS), cellulose, and Zeonex]. The compounds display very high values of singlet oxygen (1O2) production in dichloromethane. Singlet oxygen production was also evaluated in the doped matrices, being the highest in PS and with an exciting increase on PS microspheres. Density functional theory (BP86-D3) and GFN2-xTB calculations were used to model the assembly of L and complexes 1 and 2 with the different organic matrices and rationalize the experimental findings based on the geometries, molecular electrostatic potential surfaces, and complementarity and HOMO–LUMO gaps.

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Section: Resultssupporting

confidence: 58%

Ligand and Gold(I) Fluorescein–AIEgens as Photosensitizers in Solution and Doped Polymers

et al. 2023

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“…As expected, similar values for the dispersion of pure porphyrin crystals (ϕ Δ = 2.7%) and the Zn(II) MOF (ϕ Δ = 2.3%) was detected, although in the first case, the large H 2 TPyP crystals do not disperse homogeneously in the solvent, unlike the case of the MOF. These values were found to be quite low, which is the result expected in aqueous dispersions where, in comparison with other solvents, the concentration of the dissolved O 2 is low. , Nevertheless, aqueous media were used in order to maintain similar conditions to the PDT experiment. Despite the relatively low quantum yields, based on the important fluorescence decay, and the well-known photosensitizing ability of porphyrins, this experiment demonstrates that the [Zn-TPyP] n MOF is a compound with characteristics adequate to be used in PDT.…”

Section: Resultsmentioning

confidence: 81%

“…These values were found to be quite low, which is the result expected in aqueous dispersions where, in comparison with other solvents, the concentration of the dissolved O 2 is low. 44 , 45 Nevertheless, aqueous media were used in order to maintain similar conditions to the PDT experiment. Despite the relatively low quantum yields, based on the important fluorescence decay, and the well-known photosensitizing ability of porphyrins, this experiment demonstrates that the [Zn-TPyP] n MOF is a compound with characteristics adequate to be used in PDT.…”

Section: Resultsmentioning

confidence: 99%

Supercritical CO₂ Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy

et al. 2023

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A series of porous metalloporphyrin frameworks prepared from the 5,10,15,20-tetra(4-pyridyl)porphyrin (H 2 TPyP) linker and four metal complexes, M(hfac) 2 M = Cu(II), Zn(II), Co(II), and Ni(II) (hfac: 1,1,1,5,5,5-hexafluoroacetylacetonate), were obtained using supercritical CO 2 (scCO 2 ) as a solvent. All the materials, named generically as [M-TPyP] n , formed porous metal− organic frameworks (MOFs), with surface areas of ∼450 m 2 g −1 . All MOFs were formed through the coordination of the metal to the exocyclic pyridine moieties in the porphyrin linker. For Cu(II), Zn(II), and Co(II), incomplete metal coordination of the inner pyrrole ring throughout the structure was observed, giving place to MOFs with substitutional defects and leading to a certain level of disorder and limited crystallinity. These samples, prepared using scCO 2 , were precipitated as nano-to micrometric powders. Separately, a layering technique from a mixture of organic solvents was used to crystallize high-quality crystals of the Co(II) based MOF, obtained with the formula [{Co(hfac) 2 } 2 H 2 TPyP] n . The crystal structure of this MOF was elucidated by single-crystal synchrotron X-ray diffraction. The Zn(II)-based MOF was selected as a potential photodynamic therapy drug in the SKBR-3 tumoral cell line showing outstanding performance. This MOF resulted to be nontoxic, but after 15 min of irradiation at 630 nm, using either 1 or 5 μM concentration of the product, almost 70% of tumor cells died after 72 h.

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“…In particular, heavy atoms are especially relevant on luminescence since they are also very well‐known to favor the intersystem crossing (ISC) process from S 1 to T 1 excited states. This may result on a change from fluorescence to phosphorescence emission (even at room temperature, producing room temperature phosphorescent materials) or generating energy transfer from T 1 to oxygen producing singlet oxygen, 1 O 2 [11–13] …”

Section: Introductionmentioning

confidence: 99%

“…This may result on a change from fluorescence to phosphorescence emission (even at room temperature, producing room temperature phosphorescent materials) or generating energy transfer from T 1 to oxygen producing singlet oxygen, 1 O 2 . [11][12][13] Gold(I) is one of the most relevant heavy atoms that is being studied on this field thanks to the possibility not only to favor ISC process but also to establish intermolecular gold(I)•••gold(I) interactions. These interactions are responsible for the formation of large supramolecular assemblies and play a direct role also on the resulting luminescence.…”

Section: Introductionmentioning

confidence: 99%

Mono‐ and Dinuclear Gold(I) Coumarin Complexes: Luminescence Studies and Singlet Oxygen Production

et al. 2023

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The 4‐(thiolmethyl)‐7‐(diethylamino)‐2H‐chromen‐2‐one ligand has been synthesized and used as chromophore in several mono‐ and dinuclear gold(I) compounds that contain a phosphane at the second coordination position. Four final products were able to obtain in pure form containing one coumarin and one phosphane ligand in the case of PTA (1,3,5‐triaza‐7‐phosphatricyclo[3.3.1.13.7]decane) and PPh3 (triphenylphosphine); one coumarin and two gold(I)‐phosphane groups in the case of phosphane=DAPTA (3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane) and two coumarin and two gold(I) atoms in the case of phosphane=DPEphos (bis[(2‐diphenylphosphino)phenyl]ether), when it was used a diphosphane. Other diphosphane ligands used were not able to give the desired products in pure form. The luminescent properties of the compounds are governed by the fluorescence of the coumarin moiety in all compounds both for measurements carried out in solution and also immobilized in PMMA organic matrix. Phosphorescence emission can be detected in all cases at 77 K both for the uncoordinated coumarin ligand and the gold(I) derivatives, being more favoured in the presence of the gold(I) heavy atom. The compounds have been used as photosensitizers to generate 1O2 with moderate quantum yields values.

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Aggregation of gold(i) complexes: phosphorescence vs. singlet oxygen production

Abstract: Herein we report on the synthesis of six new gold(i) complexes, with a tris-naphthalene substituted tertiary phosphane bearing a secondary amine as a linker and containing different halogen groups (Cl and Br) in the naphthyl group.

Cited by 6 publications

References 49 publications

Ligand and Gold(I) Fluorescein–AIEgens as Photosensitizers in Solution and Doped Polymers

Ligand and Gold(I) Fluorescein–AIEgens as Photosensitizers in Solution and Doped Polymers

Supercritical CO₂ Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy

Mono‐ and Dinuclear Gold(I) Coumarin Complexes: Luminescence Studies and Singlet Oxygen Production

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Aggregation of gold(i) complexes: phosphorescence vs. singlet oxygen production

Abstract: Herein we report on the synthesis of six new gold(i) complexes, with a tris-naphthalene substituted tertiary phosphane bearing a secondary amine as a linker and containing different halogen groups (Cl and Br) in the naphthyl group.

Cited by 6 publications

References 49 publications

Ligand and Gold(I) Fluorescein–AIEgens as Photosensitizers in Solution and Doped Polymers

Ligand and Gold(I) Fluorescein–AIEgens as Photosensitizers in Solution and Doped Polymers

Supercritical CO2 Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy

Mono‐ and Dinuclear Gold(I) Coumarin Complexes: Luminescence Studies and Singlet Oxygen Production

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Supercritical CO₂ Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy