Photoinduced Energy and Electron Transfer in a 'Two-Point' Bound Panchromatic, Near-Infrared-Absorbing Bis-styrylBODIPY(Zinc Porphyrin)2 - Fullerene Self-Assembled Supramolecular Conjugate.

Structurally well-defined self-assembled supramolecular multi-modular donor-acceptor conjugates play a significant role in furthering our understanding of photoinduced energy and electron transfer events occurring in nature, e. g., in the antenna-reaction centers of photosynthesis and their applications in light energy harvesting. However, building such multi-modular systems capable of mimicking the early events of photosynthesis has been synthetically challenging, causing a major hurdle for its growth. Often, multi-modularity is brought in by combining both covalent and noncovalent approaches. In the present study, we have developed such an approach wherein a π-extended conjugated molecular cleft, two zinc(II)porphyrin bearing bisstyrylBODIPY (dyad, 1), has been synthesized. The binding of 1 via a 'two-point' metal-ligand coordination of a bis-pyridyl fulleropyrrolidine (2), forming a stable self-assembled supramolecular complex (1 : 2), has been established. The self-assembled supramolecular complex has been fully characterized by a suite of physico-chemical methods, including TD-DFT studies. From the established energy diagram, both energy and electron transfer events were envisioned. In dyad 1, selective excitation of zinc(II)porphyrin leads to efficient singlet-singlet excitation transfer to (bisstyrly)BODIPY with an energy transfer rate constant, kEnT of 2.56×1012 s-1. In complex 1 : 2, photoexcitation of zinc(II)porphyrin results in ultrafast photoinduced electron transfer with a charge separation rate constant, kCS of 2.83×1011 s-1, and a charge recombination rate constant, kCR of 2.51×109 s-1. For excitation at 730 nm corresponding to bisstyrylBODIPY, similar results are obtained, where a biexponential decay yielded estimated values of kCS 3.44×1011 s-1 and 2.97×1010 s-1, and a kCR value of 2.10×1010 s-1. The newly built self-assembled supramolecular complex has been shown to successfully mimic the early events of the photosynthetic antenna-reaction center events.

Outsourcing Intersystem Crossing without Heavy Atoms: Energy Transfer Dynamics in PyridoneBODIPY-C60 Complexes.

The excited state dynamics in two fully characterized pyridoneBODIPY-fullerene complexes were investigated using time-resolved spectroscopy. Photoexcitation was initially localized on the pyridoneBODIPY chromophore. The energy was rapidly transferred to the fullerene, which subsequently underwent ISC to form a triplet state and returned the energy to the pyridoneBODIPY via triplet-triplet energy transfer. This ping-pong energy transfer mechanism resulted in efficient (>85%) overall conversion of the excited state pyridoneBODIPY constituent despite a complete lack of ISC in the pyridoneBODIPY in the absence of the fullerene partner. The small difference in attachment chemistry for the fullerene did not impact the initial singlet energy transfer. However, the N-methylpyrrolidine bridge did slow both the triplet-triplet energy transfer and the ultimate relaxation rate of the final triplet state when compared to an isoxazole-based bridge. The rates of each step were quantified, and computational predictions were used to complement the proposed mechanism and energetics. The result demonstrated efficient triplet sensitization of a strong chromophore that lacks significant spin-orbit coupling.

Light-Driven Hydrodefluorination of Electron-Rich Aryl Fluorides by an Anionic Rhodium-Gallium Photoredox Catalyst.

An anionic Rh-Ga complex catalyzed the hydrodefluorination of challenging C-F bonds in electron-rich aryl fluorides and trifluoromethylarenes when irradiated with violet light in the presence of H2 , a stoichiometric alkoxide base, and a crown-ether additive. Based on theoretical calculations, the lowest unoccupied molecular orbital (LUMO), which is delocalized across both the Rh and Ga atoms, becomes singly occupied upon excitation, thereby poising the Rh-Ga complex for photoinduced single-electron transfer (SET). Stoichiometric and control reactions support that the C-F activation is mediated by the excited anionic Rh-Ga complex. After SET, the proposed neutral Rh0 intermediate was detected by EPR spectroscopy, which matched the spectrum of an independently synthesized sample. Deuterium-labeling studies corroborate the generation of aryl radicals during catalysis and their subsequent hydrogen-atom abstraction from the THF solvent to generate the hydrodefluorinated arene products. Altogether, the combined experimental and theoretical data support an unconventional bimetallic excitation that achieves the activation of strong C-F bonds and uses H2 and base as the terminal reductant.

Probing Electronic Communication and Excited-State Dynamics in the Unprecedented Ferrocene-Containing Zinc MB-DIPY.

The electronic communication between two ferrocene groups in the electron-deficient expanded aza-BODIPY analogue of zinc manitoba-dipyrromethene (MB-DIPY) was probed by spectroscopic, electrochemical, spectroelectrochemical, and theoretical methods. The excited-state dynamics involved sub-ps formation of the charge-separated state in the organometallic zinc MB-DIPYs, followed by recovery of the ground state via charge recombination in 12 ps. The excited-state behavior was contrasted with that observed in the parent complex that lacked the ferrocene electron donors and has a much longer excited-state lifetime (670 ps for the singlet state). Much longer decay times observed for the parent complex without ferrocene confirm that the main quenching mechanism in the ferrocene-containing 4 is reflective of the ultrafast ferrocene-to-MB-DIPY core charge transfer (CT).

The Mars Science Laboratory (MSL) Mast cameras and Descent imager: Investigation and instrument descriptions.

The Mars Science Laboratory Mast camera and Descent Imager investigations were designed, built, and operated by Malin Space Science Systems of San Diego, CA. They share common electronics and focal plane designs but have different optics. There are two Mastcams of dissimilar focal length. The Mastcam-34 has an f/8, 34 mm focal length lens, and the M-100 an f/10, 100 mm focal length lens. The M-34 field of view is about 20° × 15° with an instantaneous field of view (IFOV) of 218 µrad; the M-100 field of view (FOV) is 6.8° × 5.1° with an IFOV of 74 µrad. The M-34 can focus from 0.5 m to infinity, and the M-100 from ~1.6 m to infinity. All three cameras can acquire color images through a Bayer color filter array, and the Mastcams can also acquire images through seven science filters. Images are ≤1600 pixels wide by 1200 pixels tall. The Mastcams, mounted on the ~2 m tall Remote Sensing Mast, have a 360° azimuth and ~180° elevation field of regard. Mars Descent Imager is fixed-mounted to the bottom left front side of the rover at ~66 cm above the surface. Its fixed focus lens is in focus from ~2 m to infinity, but out of focus at 66 cm. The f/3 lens has a FOV of ~70° by 52° across and along the direction of motion, with an IFOV of 0.76 mrad. All cameras can acquire video at 4 frames/second for full frames or 720p HD at 6 fps. Images can be processed using lossy Joint Photographic Experts Group and predictive lossless compression.