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

Determining organophosphorus pesticides in agriculture: A combined approach of ion-mobility spectrometry with robust principal component analysis and multivariate adaptive regression splines DOI

Abdollah Azad,

Mohammadreza Khanmohammadi, Mahsa Mohammadi

et al.

International Journal of Mass Spectrometry, Journal Year: 2025, Volume and Issue: unknown, P. 117407 - 117407

Published: Jan. 1, 2025

Language: Английский

Citations

1
Exploring the Activation of Atomically Precise [Pt17(CO)12(PPh3)8]2+ Clusters: Mechanism and Energetics in Gas Phase and on an Inert Surface DOI
Papri Chakraborty, Marco Neumaier, Johannes Seibel

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

Atomically precise clusters such as [Pt17(CO)12(PPh3)8]x+ (x = 1,2) (PPh3 is triphenylphosphine) are known precursors for making oxidation catalysts. However, the changes occurring to cluster upon thermal activation during formation of active catalyst poorly understood. We have used a combination hybrid mass spectrometry and surface science map decomposition [Pt17(CO)12(PPh3)8](NO3)2. High-resolution ion mobility together with DFT-based modeling were probe sequence fragmentation reactions fragment structures generated collisional excitation [Pt17(CO)12(PPh3)8]2+. This was compared desorption spectroscopy [Pt17(CO)12(PPh3)8](NO3)2 dropcast onto an inert graphite surface. In both cases, characteristic CO benzene steps observed followed at higher energy by H2 loss. behavior indicative Pt-catalyzed C–H phenyl groups partial stripping ligand shell while Pt17P8 core retained.

Language: Английский

Citations

1
Modern Electrospray Ionization Mass Spectrometry Techniques for the Characterization of Supramolecules and Coordination Compounds DOI Creative Commons
Niklas Geue

Analytical Chemistry, Journal Year: 2024, Volume and Issue: 96(19), P. 7332 - 7341

Published: April 30, 2024

Mass spectrometry is routinely used for myriad applications in clinical, industrial, and research laboratories worldwide. Developments the areas of ionization sources, high-resolution mass analyzers, tandem spectrometry, ion mobility have significantly extended repertoire spectrometrists; however, coordination compounds supramolecules, remains underexplored arguably underappreciated. Here, reader guided through different tools modern electrospray that are suitable larger inorganic complexes. All steps, from sample preparation technical details to data analysis interpretation discussed. The main target audience this tutorial synthetic chemists as well technicians/mass spectrometrists with little experience characterizing labile compounds.

Language: Английский

Citations

4
Exploring the Conformational Landscape of Poly(l-lysine) Dendrimers Using Ion Mobility Mass Spectrometry DOI Creative Commons

Florian Benoit,

Xudong Wang,

Junxiao Dai

et al.

Analytical Chemistry, Journal Year: 2024, Volume and Issue: 96(23), P. 9390 - 9398

Published: May 30, 2024

Ion mobility mass spectrometry (IM-MS) measures the mass, size, and shape of ions in same experiment, structural information is provided via collision cross-section (CCS) values. The majority commercially available IM-MS instrumentation relies on use CCS calibrants, here, we present data from a family poly(l-lysine) dendrimers explore their suitability for this purpose. In order to test these compounds, employed three different platforms (Agilent 6560 IM-QToF, Waters Synapt G2, home-built variable temperature drift tube IM-MS) used them investigate six generations two buffer gases (helium nitrogen). Each molecule gives highly discrete distribution suggestive single conformers each m/z value. DTCCSN2 values series molecules (molecular weight: 330–16,214 Da) range 182 2941 Å2, which spans that would be found by many synthetic including supramolecular compounds biopolymers. charge state were reproducible day-to-day analysis instrument, although small variations absolute between instruments. rigidity dendrimer was probed using collisionally activated high-temperature experiments, where no evidence significant change ensued. Taken together, indicates polymers are candidates calibration could also help reconcile differences measurements instrument geometries.

Language: Английский

Citations

3
Tailoring Super‐Performed Chemo‐Sensor via Simulation‐Modeling and MEMS‐Screening DOI Creative Commons
Wei Xu, Wukun Zhang,

Zhengqi Shen

et al.

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Abstract Chemo‐sensor designing involves a time‐consuming trial‐and‐error screening process, which commonly cannot lead to optimal S 4 R features (Sensitivity, Selectivity, Speed, Stability, and Reversibility). Due strong path dependence on reported groups/mechanisms, conventional chemo‐sensors often fail meet critical application demands, especially in achieving high reversibility without compromising other features. Here, three‐step screen design strategy is developed for gaining customized chemo‐sensors, through Structure modeling; MEMS (Micro Electro Mechanical Systems) analysis, Performance verification . With such strategy, the coordination hanging anion mechanism screened out reversible nerve agent detection shows emission enhancement by 25.8 times with DCP, ultrasensitive vapor phase (5.7 ppb), rapid response(10 s) recovery speed (20 s). Such tailored new organic will probably play an important role developing high‐performance sensing system future.

Language: Английский

Citations

0
Discovery of a Ferromagnetic Nickel Chalcogenide Nanocluster Ni3S3H(PEt3)5 DOI Creative Commons
Xilai Li, Xiaofeng Wu, N. R. Dilley

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Atomically precise ligated nanoclusters (NC) are promising cluster-based materials with novel molecular architectures and tunable magnetic properties. Herein, the synthesis characterization of a nickel sulfide NC Ni3S3H(PEt3)5 (PEt3 = triethylphosphine) distinct properties reported. Magnetization measurements reveal its moment 1.5 µB in solid phase, consistent existence one unpaired electron predicted by density functional theory (DFT) calculations. Additionally, experimental indicate presence ferromagnetic ordering within each strong coercivity at temperatures below 20 K. Ion mobility-mass spectrometry is employed conjunction DFT calculations collision cross-section simulations to investigate structure isolated Ni3S3H(PEt3)5. Theoretical studies show that [Ni3S3H(PEt3)5]+ has planar Ni3S3 core where three Ni atoms arranged triangle bridging S residing same plane. This preserved both solution phases, which confirmed spectroscopic all spins sites aligned parallel, confirming coupling. Overall, this study provides key insights into Ni3S3H(PEt3)5, will facilitate design new NC-based materials.

Language: Английский

Citations

0
Advanced Mass Spectrometry Techniques for the Characterization of Carbohydrates DOI
Niklas Geue, Caitlin Walton‐Doyle,

Eleonora Renzi

et al.

Handbook of experimental pharmacology, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Observation of Structural Isomers and Isomerization of an Atom-Precise Gold Hydride Nanocluster Using Ion Mobility Spectrometry DOI
Jia Dong, Patrick Weis,

Vaibhav S. Wani

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 4975 - 4981

Published: May 12, 2025

Ion mobility spectrometry (IMS) is a powerful technique to determine structures and isomers of gas phase clusters complex molecules. It also valuable tool investigate ligand-protected atom-precise nanoclusters that cannot be readily crystallized examined by X-ray diffraction. Here we use IMS study diphosphine-protected gold hydride nanocluster, [Au22H3(dppee)7]3+ (dppee = bis(2-diphenylphosphino)ethyl ether), which was synthesized previously hypothesized contain two Au11 units with different bridging ligands. Surprisingly, our data revealed the coexistence structural in as-synthesized product population ∼85% for main isomer ∼15% minor isomer. The are found interconvertible at high activation voltages. Comparison between theoretical calculations confirm consist one three ligands, respectively. isomerization process uncovered this work provide opportunities structure-property relationship atomically precise metal nanoclusters.

Language: Английский

Citations

0
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
Modern Electrospray Ionization Mass Spectrometry Techniques for the Characterisation of Supramolecules and Coordination Compounds DOI Creative Commons
Niklas Geue

Published: April 8, 2024

Mass spectrometry is routinely used for myriad applications in clinical, industrial, and research laboratories worldwide. Developments the areas of ionisation sources, high-resolution mass analysers, tandem spectrometry, ion mobility have significantly extended repertoire spectrometrists, however coordination compounds supramolecules, remains underexplored arguably underappreciated. Here, reader guided through different tools modern electrospray ionization that are suitable larger inorganic complexes. All steps, from sample preparation technical details to data analysis interpretation discussed. The main target audience this tutorial synthetic chemists as well technicians/mass spectrometrists with little experience characterising labile compounds.

Language: Английский

Citations

1