Understanding the role of intermolecular interaction on through-space charge transfer characteristics in π-stacked molecular systems is central to the rational design of electronic materials. However, a quantitative study of charge transfer in such systems is often difficult because of poor control over molecular morphology. Here we use the core-hole clock implementation of resonant photoemission spectroscopy to study the femtosecond charge-transfer dynamics in cyclophanes, which consist of two precisely stacked π-systems held together by aliphatic chains. We study two systems, [2,2]paracyclophane (22PCP) and [4,4]paracyclophane (44PCP), with inter-ring separations of 3.0 and 4.0 Å, respectively. We find that charge transfer across the π-coupled system of 44PCP is 20 times slower than in 22PCP. We attribute this difference to the decreased inter-ring electronic coupling in 44PCP. These measurements illustrate the use of core-hole clock spectroscopy as a general tool for quantifying through-space coupling in π-stacked systems.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1038/ncomms2083 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Cathode Design Based on Nitrogen Redox and Linear Coordination of Cu Center for All-Solid-State Fluoride-Ion Batteries.
J Am Chem Soc
January 2025
Graduate School of Human and Environmental Studies, Kyoto University, Sakyo, Kyoto 606-8501, Japan.
All-solid-state fluoride-ion batteries (FIBs) have attracted extensive attention as candidates for next-generation energy storage devices; however, promising cathodes with high energy density are still lacking. In this study, CuN is investigated as a cathode material for all-solid-state fluoride-ion batteries, which offers enough anionic vacancies around the 2-fold coordinated Cu center for F intercalation, thereby enabling a multielectron-transferred fluorination process. The contribution of both cationic and anionic redox to charge compensation, in particular, the generation of molecular nitrogen species in highly charged states, has been proved by several synchrotron-radiation-based spectroscopic technologies.
View Article and Find Full Text PDFPhotoinduced Long-Distance Charge Transfer in Silicanes: The Stacking Matters.
Nano Lett
January 2025
Department of Chemistry, York University, Toronto, Ontario M3J1P3, Canada.
The generation of interlayer charge transfer excitons upon photoexcitation is strongly desirable for two-dimensional (2D) materials stacked through van der Waals interactions. In this work, we investigate photoinduced charge transfer in silicanes (SiH) with three typical stackings. A concept of the regional natural hole orbital and its conjugated particle orbital is developed to characterize excited states in solids.
View Article and Find Full Text PDFA mononuclear iron(II) complex constructed using a complementary ligand pair exhibits intrinsic luminescence-spin-crossover coupling.
Dalton Trans
January 2025
State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, No. 2 Linggong Road, Dalian 116024, P. R. China.
Molecular materials that exhibit synergistic coupling between luminescence and spin-crossover (SCO) behaviors hold significant promise for applications in molecular sensors and memory devices. However, the rational design and underlying coupling mechanisms remain substantial challenges in this field. In this study, we utilized a luminescent complementary ligand pair as an intramolecular luminophore to construct a new Fe-based SCO complex, namely [FeLL](BF)·HO (1-Fe, L is a 2,2':6',2''-terpyridine (TPY) derivative ligand and L is 2,6-di-1-pyrazol-1-yl-4-pyridinecarboxylic acid), and two isomorphic analogs (2-Co, [CoLL](BF)·HO and 3-Zn, [ZnLL](BF)·HO).
View Article and Find Full Text PDFMolecular Order Induced Charge Transfer in a C-Topological Insulator Moiré Heterostructure.
Nano Lett
January 2025
Institut für Festkörperelektronik, Technische Universität Wien, Gußhausstraße 25, 1040 Vienna, Austria.
We synthesized and spectroscopically investigated monolayer (ML) C on the topological insulator (TI) BiTe. This C/BiTe heterostructure is characterized by an excellent translational order in a novel (4 × 4) C superstructure on a (9 × 9) cell of BiTe. Angle-resolved photoemission spectroscopy (ARPES) of C/BiTe reveals that ML C accepts electrons from the TI at room temperature, but no charge transfer occurs at low temperatures.
View Article and Find Full Text PDFA metal-organic framework with mixed electron donor and electron acceptor ligands for efficient lithium-ion storage.
Chem Commun (Camb)
January 2025
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
Electron donor tetrathiafulvalene (TTF) and electron acceptor naphthalene diimide (NDI) derivatives were used to synthesize a 3D Zn-TTF/NDI-MOF. Multiple redox active sites and charge transfer endow the pristine MOF anode with excellent rate behavior and long term cycling performance (with an average specific capacity of 956 mA h g at 1 A g over 600 cycles). This study highlights the great potential of elaborately-designed MOFs for developing efficient anode materials.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!