Oxygen quenching of electronically excited hexanuclear molybdenum and tungsten halide clusters

Jackson, Julie; Turró, Claudia; Newsham, Mark D.; Nocera, Daniel G.

doi:10.1021/j100374a029

Cited by 159 publications

(161 citation statements)

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“…3 The only notable difference among the prepared complexes is a higher Φ L for 2; however, there is no evident correlation between the photophysical properties of 1− 3 and the acidities of closo-dicarbaborane C-carboxylic acids (pK a (1-HOOC-1,2-closo-C 2 B 10 H 11 ) = 13.9, pK a (1-HOOC-1,7-closo-C 2 B 10 H 11 ) = 16.2, pK a (1-HOOC-1,12-closo-C 2 B 10 H 11 ) = 16.7 in acetonitrile). 22 Overall, compounds 1−3 displayed luminescence properties similar to those of (n-B u 4 N ) 2 7 Preparation and Characterization of Water Dispersions. The luminescent hydrogel particles, 2@poly-β-CD, were prepared by self-assembly of β-cyclodextrin polymer and 2 in a water/THF mixture (1:1, v/v), followed by the evaporation of THF.…”

Section: Inorganic Chemistrymentioning

confidence: 92%

Luminescent Hydrogel Particles Prepared by Self-Assembly of β-Cyclodextrin Polymer and Octahedral Molybdenum Cluster Complexes

et al. 2014

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A series of luminescent octahedral molybdenum cluster complexes were obtained by treating Na2[Mo6I8(OMe)6] with icosahedral closo-dicarbaborane C-carboxylic acids in refluxing tetrahydrofuran. The study of the photophysical properties of Na2[Mo6I8(1-OOC-1,2-closo-C2B10H11)6] (1), Na2[Mo6I8(1-OOC-1,7-closo-C2B10H11)6] (2), and Na2[Mo6I8(1-OOC-1,12-closo-C2B10H11)6] (3) in acetonitrile revealed a red luminescence with high quantum yields up to 0.93 for 2, an efficient quenching of the luminescence by oxygen, and high quantum yields of singlet oxygen formation of approximately 0.7. Self-assembly between compound 2 and β-cyclodextrin polymer led to monodisperse hydrogel particles with a diameter of approximately 200 nm and unchanged luminescence spectra and kinetics features over 14 days. In contrast, bare cluster complex 2 in water formed aggregates and hydrolyzed over the time as indicated by a progressive red shift of the luminescence maxima. The invariance of key photophysical parameters of the hydrogel particles coupled with a high oxygen sensitivity of the luminescence are attractive features for long-term biological experiments involving optical oxygen probing. In addition, this hydrogel is a singlet oxygen sensitizer in water with promising properties for photodynamic therapy.

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Section: Inorganic Chemistrymentioning

confidence: 92%

Luminescent Hydrogel Particles Prepared by Self-Assembly of β-Cyclodextrin Polymer and Octahedral Molybdenum Cluster Complexes

et al. 2014

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“…Firstly, similarly to their structural analogues, hexarhenium clusters [{Re 6 Q 8 }L 6 ] m (Q = S or Se), these complexes demonstrate high chemical and photostability of the cluster cores {Mo 6 X 8 } 4+ that are primarily responsible for their triplet excited state photoluminescence (i.e. 4,5,11,15 Additionally, the metal cluster complexes can also act as powerful photosensitisers in the singlet oxygen ( 1 O 2 ) generation, [5][6][7][8][16][17][18] which makes them especially interesting for applications associated with the generation of singlet oxygen in vivo, such as, for example, photodynamic therapy (PDT). Secondly, their broad emission spectra extend in the red/near infra-red region (from ∼550 to more than 950 nm) 4-13 overlapping the so called "optical tissue window" (650 − 900 nm), where the boundaries of the region are defined by the minimal light absorption of hemoglobin (< 650 nm) and water (> 900 nm).…”

Section: Introductionmentioning

confidence: 99%

Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {Mo₆I₈}⁴⁺ metal clusters

et al. 2016

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Silica nanoparticles (SNPs) doped by hexanuclear molybdenum cluster complexes [{Mo6X8}L6] n (X = Cl, Br, or I; L = various inorganic or organic ligands) have been recently suggested as materials with a high potential for biomedical applications due to both the outstanding photoluminescent properties and the ability to efficiently generate singlet oxygen upon photoirradiation. However, no studies were undertaken so far to prove this concept. Therefore, here we examined the potential of photoluminescent SNPs doped by {Mo6I8} 4+ for such applications as bioimaging and photodynamic therapy using human epidermoid larynx carcinoma (Hep-2) cell line as a model. Our results demonstrated both: (i) significant luminescence from cells with internalised molybdenum cluster-doped SNPs combined with the low cytotoxicity of particles in the darkness and (ii) significant cytotoxicity of the particles upon photoirradiation. Thus, this research provides strong experimental evidence for high potential of molybdenum-cluster-doped materials in such biomedical applications as optical bioimaging, biolabeling and photodynamic therapy.

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“…[8] The L a ligands are easily replaceable and affect the inherent properties of cluster complexes. [9,10] A weak absorption in the visible region can be overcame by using complexes containing the Mo 6 I i 8 cluster core characterized by an absorption onset that extends to the red spectral region. Φ Δ .…”

Section: Introductionmentioning

confidence: 99%

A Highly Luminescent Hexanuclear Molybdenum Cluster – A Promising Candidate toward Photoactive Materials

et al. 2012

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Oxygen quenching of electronically excited hexanuclear molybdenum and tungsten halide clusters

Cited by 159 publications

References 4 publications

Luminescent Hydrogel Particles Prepared by Self-Assembly of β-Cyclodextrin Polymer and Octahedral Molybdenum Cluster Complexes

Luminescent Hydrogel Particles Prepared by Self-Assembly of β-Cyclodextrin Polymer and Octahedral Molybdenum Cluster Complexes

Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {Mo₆I₈}⁴⁺ metal clusters

A Highly Luminescent Hexanuclear Molybdenum Cluster – A Promising Candidate toward Photoactive Materials

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Oxygen quenching of electronically excited hexanuclear molybdenum and tungsten halide clusters

Cited by 159 publications

References 4 publications

Luminescent Hydrogel Particles Prepared by Self-Assembly of β-Cyclodextrin Polymer and Octahedral Molybdenum Cluster Complexes

Luminescent Hydrogel Particles Prepared by Self-Assembly of β-Cyclodextrin Polymer and Octahedral Molybdenum Cluster Complexes

Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {Mo6I8}4+ metal clusters

A Highly Luminescent Hexanuclear Molybdenum Cluster – A Promising Candidate toward Photoactive Materials

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Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {Mo₆I₈}⁴⁺ metal clusters