Nanoparticle-Mediated Intervalence Transfer

Chen, Wei; Chen, Shaowei; Ding, Fazhu; Wang, Haobin; Brown, Lauren E.; Konopelski, Joseph P.

doi:10.1021/ja803887b

Cited by 59 publications

(102 citation statements)

References 51 publications

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“…This suggests that on average there are approximately 20 pyrene functional groups per nanoparticle. 9 UV-visible absorption measurements were then carried out. Figure 1 depicts the optical absorption spectra of the RudC8, RudVPy, and RudAPy nanoparticles, along with those of 1-vinylpyrene and 1-allylpyrene.…”

Section: Resultsmentioning

confidence: 99%

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

et al. 2009

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Ruthenium nanoparticles functionalized with pyrene moieties were prepared by olefin metathesis reactions of carbenestabilized nanoparticles with 1-vinylpyrene and 1-allylpyrene (referred to as RudVPy and RudAPy, respectively). 1 H NMR spectroscopic measurements showed that the surface concentration of the pyrene moieties was 26.4 and 22.9%, respectively. In fluorescence measurements, RudVPy nanoparticles exhibited two prominent emission bands at 392 and 490 nm, very similar to those of (E)-1,2-di(pyren-1-yl)ethene, suggesting that the particle-bound pyrene moieties might behave equivalently to pyrene dimers with a conjugated linker by virtue of the Rudcarbene π bonds. In sharp contrast, RudAPy nanoparticles displayed only a single emission peak at 392 nm, consistent with monomeric pyrene derivatives of 1-vinylpyrene and 1-allylpyrene. This implies that the intraparticle extended conjugation might be effectively turned off by the insertion of an sp 3 carbon into the chemical linker that bound the pyrene moieties onto the nanoparticles. In addition, RudVPy nanoparticles exhibited a rather long lifetime of the emission at 490 nm, as compared to that of the conjugated pyrene dimer, suggesting that the nanoparticles might be less prone to photobleaching. This is attributed to the neighboring organic protecting ligands that may create a more rigid chemical environment for the nanoparticle-bound pyrene moieties and thus prolong the life of the excited state, as compared to the strong electrostatic perturbations which exist in free solution when surrounded by a polar solvent.

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Section: Resultsmentioning

confidence: 99%

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

et al. 2009

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“…Vice versa, coordination on a metal surface strongly modifies the physical properties of the organic molecule. One can cite the quenching of fluorescence [156], the change in the redox behavior of ferrocenyl end-groups [157] or the change in the thermodynamic constants of acids end-groups due to cooperative effects [158], as well as the change of association constants in the case of DNA [159].…”

Section: Influence Of Ligand Coordination At the Surface Of Metal Nanmentioning

confidence: 99%

Controlled metal nanostructures: Fertile ground for coordination chemists

Amiens

Ciuculescu-Pradines

Philippot

2016

Coordination Chemistry Reviews

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“…[1] This leads to the emergence of new optical and electronic properties that are analogous to those of their dimeric derivatives.F or instance,w hen ferrocenyl moieties are bound to ruthenium nanoparticle surfaces by ruthenium-carbene (Ru = C) p bonds,e lectrochemical measurements exhibit two pairs of voltammetric peaks consistent with the well-known intervalence charge transfer (IVCT) of biferrocene derivatives bridged with conjugated chemical linkers. [1] This leads to the emergence of new optical and electronic properties that are analogous to those of their dimeric derivatives.F or instance,w hen ferrocenyl moieties are bound to ruthenium nanoparticle surfaces by ruthenium-carbene (Ru = C) p bonds,e lectrochemical measurements exhibit two pairs of voltammetric peaks consistent with the well-known intervalence charge transfer (IVCT) of biferrocene derivatives bridged with conjugated chemical linkers.…”

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Nanoparticle‐Mediated Intervalence Charge Transfer: Core‐Size Effects

Chen

Deming

et al. 2015

Angew Chem Int Ed

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Two types of platinum nanoparticles (NPs) functionalized with ethynylferrocene were prepared. The subnanometer-sized NPs (Pt10eFc) showed semiconductor-like characteristics with a bandgap of about 1.0 eV, and the other was metal-like with a core size of about 2 nm (Pt314eFc) and no significant bandgap. IR spectroscopic measurements showed a clear red-shift of the C≡C and ferrocenyl ring =C-H vibrational energies with increasing particle core size owing to enhanced intraparticle charge delocalization between the particle-bound ferrocenyl moieties. Electrochemical measurements showed two pairs of voltammetric peaks owing to intervalence charge transfer between the ferrocenyl groups on the nanoparticle surface, which was apparently weaker with Pt10 eFc than with Pt314 eFc. Significantly, the former might be markedly enhanced with UV photoirradiation owing to enhanced nanoparticle electronic conductivity, whereas no apparent effects were observed with the latter.

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Nanoparticle-Mediated Intervalence Transfer

Cited by 59 publications

References 51 publications

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation

Controlled metal nanostructures: Fertile ground for coordination chemists

Nanoparticle‐Mediated Intervalence Charge Transfer: Core‐Size Effects

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