Vibration-induced emission: Dynamic multiple intrinsic luminescence

Modulating single-molecule charge transport through external stimulus

The viscosity distribution of micellar interiors from the very center to the outer surface is dramatically varied, which has been distinguished in theoretical models, yet it remains highly challenging to quantify this issue experimentally. Herein, a series of fluorophore-substituted surfactants DPAC-Fn (n = 3, 5, 7, 9, 11, 13, and 15) are developed by functionalizing the different alkyl-trimethylammonium bromides with the butterfly motion-based viscosity sensor, N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC). The immersion depth of DPAC units of DPAC-Fn in cetrimonium bromide (C16TAB) micelles depends on the alkyl chain lengths n. From deep (n = 15) to shallow (n = 3), DPAC-Fn in C16TAB micelles exhibits efficient viscosity-sensitive dynamic multicolor emissions. With external standards for quantification, the viscosity distribution inside a C16TAB micelle with the size of ∼4 nm is changed seriously from high viscosity (∼190 Pa s) in the core center to low viscosity (∼1 Pa s) near the outer surface. This work provides a tailored approach for powerful micelle tools to explore the depth-dependent microviscosity of micellar interiors.

Exploring the Depth-Dependent Microviscosity inside a Micelle Using Butterfly-Motion-Based Fluorescent Probes.

Over the last century, quantum theories have revolutionized our understanding of material properties. One of the most striking quantum phenomena occurring in heterogeneous media is the quantum tunneling effect, where carriers can tunnel through potential barriers even if the barrier height exceeds the carrier energy. Interestingly, the tunneling process can be accompanied by the absorption or emission of light. In most tunneling junctions made of noble metal electrodes, these optical phenomena are governed by plasmonic modes, i.e., light-driven collective oscillations of surface electrons. In the emission process, plasmon excitation via inelastic tunneling electrons can improve the efficiency of photon generation, resulting in bright nanoscale optical sources. On the other hand, the incident light can affect the tunneling behavior of plasmonic junctions as well, leading to phenomena such as optical rectification and induced photocurrent. Thus, plasmonic tunneling junctions provide a rich platform for investigating light-matter interactions, paving the way for various applications, including nanoscale light sources, sensors, and chemical reactors. In this paper, we will introduce recent research progress and promising applications based on plasmonic tunneling junctions.

https://aip.scitation.org/doi/pdf/10.1063/5.0128822

Optical properties of plasmonic tunneling junctions.

Single-Molecule Functional Chips: Unveiling the Full Potential of Molecular Electronics and Optoelectronics

Single-molecule conductance measurements for 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC) may offer unique insight into the bent-to-planar photocycle between the ground and excited states. Herein, we employ DPAC derivative DPAC-SMe as the molecular prototype to fabricate single-molecule junctions using the scanning tunneling microscope break junction technique and explore photoconductance dependence on the excited-state structural/electronic changes. We find up to ∼200% conductance enhancement of DPAC-SMe under continuous 340 nm light irradiation than that without irradiation, while photoconductance disappears in the case where structural evolution of the DPAC-SMe is halted through macrocyclization. The in situ conductance modulation as pulsed 340 nm light irradiation is monitored in the DPAC-SMe-based junctions alone, suggesting that the photoconductance of DPAC-SMe stems from photoinduced intramolecular planarization. Theoretical calculations reveal that the photoinduced structural evolution brings about a significant redistribution of the electron cloud density, which leads to the appearance of Fano resonance, resulting in enhanced conductance through the DPAC-SMe-fabricated junctions. This work provides evidence of bent-to-planar photocycle-induced conductance differences at the single-molecule level, offering a tailored approach for tuning the charge transport characteristics of organic photoelectronic devices.

Photoconductance from the Bent-to-Planar Photocycle between Ground and Excited States in Single-Molecule Junctions.

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Photoconductance from the Bent-to-Planar Photocycle between Ground and Excited States in Single-Molecule Junctions.