Scanning probe microscopy makes it possible to image and spectroscopically characterize nanoscale objects, and to manipulate and excite them; even time-resolved experiments are now routinely achieved. This combination of capabilities has enabled proof-of-principle demonstrations of nanoscale devices, including logic operations based on molecular cascades , a single-atom transistor , a single-atom magnetic memory cell and a kilobyte atomic memory . However, a key challenge is fabricating device structures that can overcome their attraction to the underlying surface and thus protrude from the two-dimensional flatlands of the surface. Here we demonstrate the fabrication of such a structure: we use the tip of a scanning probe microscope to lift a large planar aromatic molecule (3,4,9,10-perylenetetracarboxylic-dianhydride) into an upright, standing geometry on a pedestal of two metal (silver) adatoms. This atypical and surprisingly stable upright orientation of the single molecule, which under all known circumstances adsorbs flat on metals, enables the system to function as a coherent single-electron field emitter. We anticipate that other metastable adsorbate configurations might also be accessible, thereby opening up the third dimension for the design of functional nanostructures on surfaces.
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http://dx.doi.org/10.1038/s41586-018-0223-y | DOI Listing |
Org Biomol Chem
January 2025
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, China.
Recent advancements in C-S bond formation electron donor-acceptor (EDA) complex photoactivation have been remarkable. EDA complexes, which are composed of electron donors and acceptors, facilitate C-S bond construction under mild conditions through single-electron transfer events upon visible light irradiation. This review highlights the utilization of various sulfur-containing substrates, including diacetoxybenzenesulfonyl (DABSO), sulfonic acids, sodium sulfinates, sulfonyl chlorides, and thiophenols, in EDA-promoted sulfonylation and thiolation reactions, covering the works published since 2017 to date.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Nanjing University, Chemistry, Xianlin 163Hao, Nanjing 210023, 210023, Nanjing, CHINA.
The simple and efficient conversion of carboxylic acids into structurally diverse organic molecules is highly desirable in chemical synthesis. This review covers recent developments in photocatalytic methodology for late-stage transformations of complex carboxylic acids and their derivatives enabled by radical decarboxylation and deoxygenation, highlighting some representative and significant contributions in this field. These advancements are categorized based on the reactivity patterns exhibited by the carboxylic acids.
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, and Discipline of Intelligent Instrument and Equipment, Xiamen University, Xiamen 361005, P. R. China.
ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes and capacity to offer novel reactivity and selectivity, represents an emerging field in organic chemistry that addresses the growing demands for environmental sustainability and synthetic efficiency. This synergistic approach permits access to a wider range of redox potentials, facilitates redox transformations under gentler electrode potentials, and decreases the use of external harsh redox reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we and others reported the first examples of modern molecular photoelectrocatalysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, Sun Yat-Sen University, Guangzhou, 510006, P. R. China.
A photochromic dysprosium-based single-molecule magnet [Dy(CyPhPO)(HO)](PMoO) ⋅ 3CyPhPO⋅HO (1-Dy) is synthesized via cocrystal engineering of a polyoxomolybdate (POMo) anion and an Ising-type cation with pseudo pentagonal bipyramidal geometry. Upon ultraviolet irradiation, Mo-to-Mo single-electron photoreduction occurs in the POMo moiety, resulting in significant changes of optical and magnetic properties. The emergence of intervalence charge-transfer transitions in heteropoly blue state 1-Dy* facilitates photothermal conversion in near-infrared region.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), ChemBioMed Interdisciplinary Research Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, P. R. China.
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