Energy and Electron Transfer in Ethynylene Bridged Perylene Diimide Multichromophores

Shape persistent perylene diimide (PDI) multichromophores incorporating ethynylene bridges have been synthesized in high yield via palladium-catalyzed Hagihara coupling, which provides compounds with no rotational or constitutional isomerism in contrast to polyphenylene dendrimers. Their excited-state pathways have been studied at the ensemble and at the single-molecule level and compared to several model compounds. In an apolar solvent, energy hopping and/or energy transfer between the chromophoric units are the dominating processes. In a polar medium, energy hopping is still operative, but electron transfer from the phenyl ethynylene bridge to the chromophore occurs if the former is connected to the bay area of PDI. This effect should be considered when further developing this type of multichromophore, as this nonradiative deactivation process might be unwanted for applications such as optical and electronic devices. At the single-molecule level, the fluorescence intensity traces are characterized by rich on-off dynamics, which we attribute to oxygen-enhanced intersystem crossing leading to the formation of a long-lived dark charge-separated state.

A surface-bound molecule that undergoes optically biased Brownian rotation

Developing molecular systems with functions analogous to those of macroscopic machine components, such as rotors, gyroscopes and valves, is a long-standing goal of nanotechnology. However, macroscopic analogies go only so far in predicting function in nanoscale environments, where friction dominates over inertia. In some instances, ratchet mechanisms have been used to bias the ever-present random, thermally driven (Brownian) motion and drive molecular diffusion in desired directions. Here, we visualize the motions of surface-bound molecular rotors using defocused fluorescence imaging, and observe the transition from hindered to free Brownian rotation by tuning medium viscosity. We show that the otherwise random rotations can be biased by the polarization of the excitation light field, even though the associated optical torque is insufficient to overcome thermal fluctuations. The biased rotation is attributed instead to a fluctuating-friction mechanism in which photoexcitation of the rotor strongly inhibits its diffusion rate.

Multicolor Fluorescence Nanoscopy in Fixed and Living Cells by Exciting Conventional Fluorophores with a Single Wavelength

Current far-field fluorescence nanoscopes provide subdiffraction resolution by exploiting a mechanism of fluorescence inhibition. This mechanism is implemented such that features closer than the diffraction limit emit separately when simultaneously exposed to excitation light. A basic mechanism for such transient fluorescence inhibition is the depletion of the fluorophore ground state by transferring it (via a triplet) in a dark state, a mechanism which is workable in most standard dyes. Here we show that microscopy based on ground state depletion followed by individual molecule return (GSDIM) can effectively provide multicolor diffraction-unlimited resolution imaging of immunolabeled fixed and SNAP-tag labeled living cells. Implemented with standard labeling techniques, GSDIM is demonstrated to separate up to four different conventional fluorophores using just two detection channels and a single laser line. The method can be expanded to even more colors by choosing optimized dichroic mirrors and selecting marker molecules with negligible inhomogeneous emission broadening

Ground-based and JWST Observations of SN 2022pul: II. Evidence from Nebular Spectroscopy for a Violent Merger in a Peculiar Type-Ia Supernova

International audienceWe present an analysis of ground-based and JWST observations of SN 2022pul, a peculiar "03fg-like" (or "super-Chandrasekhar") Type Ia supernova (SN Ia), in the nebular phase at 338 d post explosion. Our combined spectrum continuously covers 0.4-14 $\mu$m and includes the first mid-infrared spectrum of an 03fg-like SN Ia. Compared to normal SN Ia 2021aefx, SN 2022pul exhibits a lower mean ionization state, asymmetric emission-line profiles, stronger emission from the intermediate-mass elements (IMEs) argon and calcium, weaker emission from iron-group elements (IGEs), and the first unambiguous detection of neon in a SN Ia. Strong, broad, centrally peaked [Ne II] at 12.81 $\mu$m was previously predicted as a hallmark of "violent merger'' SN Ia models, where dynamical interaction between two sub-$M_{\text{Ch}}$ white dwarfs (WDs) causes disruption of the lower mass WD and detonation of the other. The violent merger scenario was already a leading hypothesis for 03fg-like SNe Ia; in SN 2022pul it can explain the large-scale ejecta asymmetries seen between the IMEs and IGEs and the central location of narrow oxygen and broad neon. We modify extant models to add clumping of the central ejecta to better reproduce the optical iron emission, and add mass in the innermost region ($< 2000$ km s$^{-1}$) to account for the observed narrow [O I] $\lambda\lambda6300$, 6364 emission. A violent WD-WD merger explains many of the observations of SN 2022pul, and our results favor this model interpretation for the subclass of 03fg-like SN Ia

Ground-based and JWST Observations of SN 2022pul: II. Evidence from Nebular Spectroscopy for a Violent Merger in a Peculiar Type-Ia Supernova

International audienceWe present an analysis of ground-based and JWST observations of SN 2022pul, a peculiar "03fg-like" (or "super-Chandrasekhar") Type Ia supernova (SN Ia), in the nebular phase at 338 d post explosion. Our combined spectrum continuously covers 0.4-14 $\mu$m and includes the first mid-infrared spectrum of an 03fg-like SN Ia. Compared to normal SN Ia 2021aefx, SN 2022pul exhibits a lower mean ionization state, asymmetric emission-line profiles, stronger emission from the intermediate-mass elements (IMEs) argon and calcium, weaker emission from iron-group elements (IGEs), and the first unambiguous detection of neon in a SN Ia. Strong, broad, centrally peaked [Ne II] at 12.81 $\mu$m was previously predicted as a hallmark of "violent merger'' SN Ia models, where dynamical interaction between two sub-$M_{\text{Ch}}$ white dwarfs (WDs) causes disruption of the lower mass WD and detonation of the other. The violent merger scenario was already a leading hypothesis for 03fg-like SNe Ia; in SN 2022pul it can explain the large-scale ejecta asymmetries seen between the IMEs and IGEs and the central location of narrow oxygen and broad neon. We modify extant models to add clumping of the central ejecta to better reproduce the optical iron emission, and add mass in the innermost region ($< 2000$ km s$^{-1}$) to account for the observed narrow [O I] $\lambda\lambda6300$, 6364 emission. A violent WD-WD merger explains many of the observations of SN 2022pul, and our results favor this model interpretation for the subclass of 03fg-like SN Ia