Nanohoops Favour Light‐Induced Energy Transfer over Charge Separation in Porphyrin/[10]CPP/Fullerene Rotaxanes DOI Creative Commons

Fabian Schwer,

Simon Zank,

Markus Freiberger

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 24, 2024

Abstract [2]Rotaxanes offer unique opportunities for studying and modulating charge separation energy transfer, because the mechanical bond allows robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C 60 bis‐adduct complex two zinc porphyrin stoppers to address how movable nanohoop affects light‐induced transfer between rotaxane subcomponents. We found that neither parent [10]CPP nor its electron‐deficient analogue aza[10]CPP actively participate in separation. contrast, nanohoops completely prevented through‐space This result is likely due supramolecular “shielding”, was observed thread acted as reference dyad. On other hand, suppression electron allowed observation from triplet fullerene state with lifetime ca. 25 μs. The presence interlocked therefore leads dramatic switch transfer. suggest our results explain observations made by others photovoltaic devices may pave way toward strategic uses mechanically architectures feature (triplet)

Language: Английский

Conformational Landscapes and Energetics of Carbon Nanohoops and their Ring-in-Ring Complexes DOI Creative Commons
Niklas Geue,

Markus Freiberger,

Stefan Frühwald

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(26), P. 6805 - 6811

Published: June 24, 2024

Carbon nanohoops are promising precursors for the synthesis of nanotubes, whose structural dynamics not well understood. Here, we investigate conformational landscape and energetics cycloparaphenylenes (CPPs), a methylene-bridged CPP carbon nanobelt. These can form host-guest complexes with other rings, understanding their structure is crucial predicting properties identifying potential applications. We used combination ion mobility, tandem mass spectrometry, density functional theory to characterize ring-in-ring complexes, following conformations disassembly from intact fragment ions. Our results show integrity complexes. They also reveal interesting trends in size, packing density, stability, between [6]CPP, CPP, nanobelt as guests Taken together, our work illustrates how spectrometry data help unravel rules that govern formation nanohoop assemblies.

Language: Английский

Citations

2
Nanohoops Favour Light‐Induced Energy Transfer over Charge Separation in Porphyrin/[10]CPP/Fullerene Rotaxanes DOI Creative Commons

Fabian Schwer,

Simon Zank,

Markus Freiberger

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 24, 2024

[2]Rotaxanes offer unique opportunities for studying and modulating charge separation energy transfer, because the mechanical bond allows robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C

Language: Английский

Citations

1
Optimisation of dynamic nuclear polarisation using “off-the-shelf” Gd(iii)-based polarising agents DOI Creative Commons
Daniel J. Cheney, Paolo Cerreia Vioglio, Adam Brookfield

et al.

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A range of simple gadolinium salts has been demonstrated to be suitable for use as polarising agents dynamic nuclear polarisation. The concentrations providing the optimum signal enhancements were also identified.

Language: Английский

Citations

0
Nanohoops Favour Light‐Induced Energy Transfer over Charge Separation in Porphyrin/[10]CPP/Fullerene Rotaxanes DOI Creative Commons

Fabian Schwer,

Simon Zank,

Markus Freiberger

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 24, 2024

Abstract [2]Rotaxanes offer unique opportunities for studying and modulating charge separation energy transfer, because the mechanical bond allows robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C 60 bis‐adduct complex two zinc porphyrin stoppers to address how movable nanohoop affects light‐induced transfer between rotaxane subcomponents. We found that neither parent [10]CPP nor its electron‐deficient analogue aza[10]CPP actively participate in separation. contrast, nanohoops completely prevented through‐space This result is likely due supramolecular “shielding”, was observed thread acted as reference dyad. On other hand, suppression electron allowed observation from triplet fullerene state with lifetime ca. 25 μs. The presence interlocked therefore leads dramatic switch transfer. suggest our results explain observations made by others photovoltaic devices may pave way toward strategic uses mechanically architectures feature (triplet)

Language: Английский

Citations

0