Aggregation-Induced Energy Transfer in a Decanuclear Os(II)/Ru(II) Polypyridine Light-Harvesting Antenna Dendrimer

Arrigo, Antonino; Puntoriero, Fausto; Ganga, Giuseppina La; Campagna, Sebastiano; Burian, Max; Bernstorff, Sigrid; Amenitsch, Heinz

doi:10.1016/j.chempr.2017.06.002

Cited by 31 publications

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“…In both these species, photo‐induced downhill energy transfer processes occur from both singlet and triplet states in non‐ equilibrated excited states, in the femtosecond time scale. [ 53–55 ]…”

Section: Figurementioning

confidence: 99%

New Hybrid Light Harvesting Antenna Based on Silicon Nanowires and Metal Dendrimers

Leonardi

Nastasi

Morganti

et al. 2020

Advanced Optical Materials

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The realization of low‐cost silicon (Si) light harvesting antennas, made with industrially compatible technology and implementable in current devices, represents a goal with a tremendous impact for several commercial applications. For the first time, the use of Si nanowires (NWs) as energy donor in a light harvesting antenna is demonstrated. Through a detailed study of the optical properties, an energy transfer process from the NWs to the dyes is reported here. In this paper, the realization of this novel hybrid material based on the luminescence of ultra‐thin Si NWs and dyes demonstrates the potential of these systems for the transfer of light, opening the route to several strategic applications from photonics to photovoltaics, sensors, and bio‐imaging.

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Section: Figurementioning

confidence: 99%

New Hybrid Light Harvesting Antenna Based on Silicon Nanowires and Metal Dendrimers

Leonardi

Nastasi

Morganti

et al. 2020

Advanced Optical Materials

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“…In order to construct an aerial for light harvesting, a multicomponent system involving numerous organized chromophores is required, which can absorb the incident light and undergo energy transfer to channel the excitation energy to a central acceptor group . In the past two decades, significant effort has been applied to supramolecular approaches toward the design and synthesis of multichromophoric structures capable of serving as antennas in synthetic systems for solar energy conversion . Dendrimers are ideal structures to use for the organization of various photoactive species in a restricted space, as this can be done rationally to design a planned pattern with specific properties.…”

Section: Light‐harvesting Dendrimer Systemsmentioning

confidence: 99%

Advances in Light‐Emitting Dendrimers

Abd‐El‐Aziz

Abdelghani

Wagner

et al. 2018

Macromol. Rapid Commun.

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with increasing generation), or even at the branching sites. Such dendrimeric structures with incorporated chromophores provide a mimic of the photosynthetic light-harvesting system, in which antenna chromophores surround the inner reaction center. [35][36][37][38] Each photoactive group within a dendrimer can show quite different emission and energy-transfer properties compared with those of the same chromophore within a small molecule (or as a separate free molecule itself), as a result of the close spatial proximity to neighboring moieties. For instance, in well-designed dendrimers, photoexcited chromophores can undergo energy transfer to other units, funneling the energy through the antenna framework toward the core, which can serve as the basis for solar energy conversion, [39,40] luminescent sensors, [41,42] and photoinduced electron transfer (PET) between units of the dendrimers. [43][44][45] This process can also result in the useful formation of excimer and exciplex species within the dendrimer, which will exhibit vastly different emission wavelengths. [46][47][48] Furthermore, dendrimers which contain metal ions have been generated to combine the redox properties of metals with other dendrimeric properties. [27,[49][50][51][52][53][54] In this review we will focus on light-harvesting dendrimeric materials with many illustrative examples. DendrimersThe design of dendrimers with various chromophores has attracted significant attention in light of the dual effect of the luminescence of the chromophores and the morphology of the synthesized dendrimers. Recent developments in this field stem from their wide potential applications, including organic light-emitting diodes, photonic switches and upconversion lasers, as well as sensors and electronic devices. The focus of this comprehensive review is on the design and properties of various classes of lightharvesting dendrimeric materials.

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“…A recent breakthrough along this direction is the recent discovery that light‐harvesting second generation dendrimers based on Ru II and Os II polypyridine complexes self‐aggregate in acetonitrile solution, even at concentrations as low as 10 –5 m –1 , and bring about aggregation‐induced energy transfer. This was demonstrated by a combination of various experiments, including steady‐state and time‐resolved absorption and luminescence spectroscopy and small angle X‐ray scattering (SAXS) using synchrotron light pulse . The aggregation‐induced energy transfer was proposed to be the result of inter‐dendrimer electronic interactions involving electronic energy donors and acceptors of different dendrimers (rate constant of interdendrimer energy transfer, 18 ps).…”

Section: Aggregation Propertiesmentioning

confidence: 99%

“…Schematization of the aggregation‐induced interdendrimer energy transfer occurring in OsRu9 . For more details, see ref …”

Section: Aggregation Propertiesmentioning

confidence: 99%

“…Here we review the fundamental steps that contributed to the build‐up of photo‐ and redox‐active metal dendrimers prepared and studied by our team along the years, as well as the recent use of some of these compounds for photoinduced water oxidation and, even more recently, the discover of the properties of self‐aggregation of the second generation metal dendrimers, with interesting consequences on the photoinduced energy migration between aggregated dendrimers …”

Section: Introductionmentioning

confidence: 99%

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Photo‐ and Redox‐Active Metal Dendrimers: A Journey from Molecular Design to Applications and Self‐Aggregated Systems

et al. 2018

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The scientific adventure starting from simple dinuclear ruthenium(II) complexes and leading to the design, preparation, and study of photo-and redox-active polynuclear metal dendrimers capable of performing useful photo-driven processes is reviewed through decades of activity. The recent appli- [a] 3887 cations of luminescent metal dendrimers in the field of artificial photosynthesis -in particular as far as the photochemical water oxidation process is concerned -and their very recently revealed self-aggregating properties, including concentrationdependent photoinduced energy transfer, are also shown. the investigation of intercomponent photoinduced energy and electron-transfer processes. The simultaneous growth of supramolecular photochemistry [11] was indeed significantly powered by such studies, and an evolution towards larger multicomponent assembled systems appeared almost obvious. Scheme 1. Structural formulas of the polypyridine ligands mainly used for the synthesis of the metal dendrimers here described and their representations, used in the following figures.Within such a scenario, our research group started a collaboration with the groups of Vincenzo Balzani in Bologna and of Gianfranco Denti in Pisa, with the aim of building up unprecedented methods toward the synthesis of metal complexes of high nuclearity, having in mind some guidelines for preparing supramolecular assemblies capable of exhibiting made-to-order properties. In particular, photoinduced intramolecular energy transfer and predetermined redox patterns were among the properties we were looking for, since such properties were essential to open the way to artificial antenna systems for light harvesting purposes and for multiple charge storage. After the initial studies, that led us to synthesize and investigate the lumi-Microreview nescence properties and redox behavior of -among othersdinuclear, trinuclear, tetranuclear, hexanuclear, heptanuclear, Sebastiano Campagna received his Laurea in Chemistry from the University of Messina in 1983. Since 1985 to 1997 he worked in the Photochemistry group led by Vincenzo Balzani at the University of Bologna. In 1998 he joined the Faculty of Science of the University of Messina, where he became full professor in 2002. His research interests include photochemistry and photophysics of coordination compounds and supramolecular species, photoinduced electron and energy transfer, and artificial photosynthesis. Giuseppina La Ganga is post-doc student at University of Messina. She received her master degree in 2009 and received her PhD in Chemistry in 2014 from the University of Messina, working in the group of Prof. Sebastiano Campagna on supramolecular photochemistry. Her scientific interest is focused on renewable energies, with particular emphasis on the generation of solar fuels. She has developed and studied in detail various kinds of sensitizer-antenna dyes and multi-electron catalysts for water oxidation. Ambra Cancelliere obtained her Master degree in Chemistry in 2016 from the University of Messina...

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Aggregation-Induced Energy Transfer in a Decanuclear Os(II)/Ru(II) Polypyridine Light-Harvesting Antenna Dendrimer

Cited by 31 publications

References 42 publications

New Hybrid Light Harvesting Antenna Based on Silicon Nanowires and Metal Dendrimers

New Hybrid Light Harvesting Antenna Based on Silicon Nanowires and Metal Dendrimers

Advances in Light‐Emitting Dendrimers

Photo‐ and Redox‐Active Metal Dendrimers: A Journey from Molecular Design to Applications and Self‐Aggregated Systems

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