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Rankin Odgaard posted an update 4 hours, 54 minutes ago
Planar chiral structures respond differently for oppositely handed incident light, and thus can produce extraordinary chiroptical effects such as circular conversion dichroism (CCD) and asymmetric transmission (AT). Such chiroptical effects are powerful tools to realize the fundamental principle of optical spin isolation, which leads to a plethora of applications such as optical conversion diodes, chiral imaging, and sensing. Here, we demonstrate the chiroptical effects of simultaneous CCD and AT through meticulously designed single-layered achiral nanofins. Our metamolecule consists of four achiral hydrogenated amorphous silicon (a-SiH) nanofins that are carefully oriented and optimized to exhibit considerable CCD and AT. The device demonstrates a circular conversion dichroism of 55% and an asymmetric transmission of 58% at a wavelength of 633 nm. Right-hand circularly polarized light (RHCP) is completely absorbed, while left-hand circularly polarized light (LHCP) is transmitted with a polarization conversion, making it a perfect circular polarization wave isolator with negligible backscattering (due to low reflectance). This unique design and its underlying working mechanism are described comprehensively with three different techniques. These methods validate the proposed design and its methodology. For practical applications such as imaging, the proposed design realizes the Pancharatnam-Berry (PB) phase, achieving a 0-2π phase coverage for transmitted circular polarization. For the proof of concept, a metahologram is designed and demonstrated by employing the achieved full-phase control. The measured response of the fabricated metadevice not only validates the CCD and AT but also exhibits a simulated polarization conversion efficiency of up to 71% and measured efficiency up to 52%, comparable to state-of-the-art metahologram demonstrations.The rhodium-catalyzed deoxygenation and borylation of ketones with B2pin2 have been developed, leading to efficient formation of alkenes, vinylboronates, and vinyldiboronates. These reactions feature mild reaction conditions, a broad substrate scope, and excellent functional-group compatibility. Mechanistic studies support that the ketones initially undergo a Rh-catalyzed deoxygenation to give alkenes via boron enolate intermediates, and the subsequent Rh-catalyzed dehydrogenative borylation of alkenes leads to the formation of vinylboronates and diboration products, which is also supported by density functional theory calculations.The Ni-catalyzed reaction of ortho-fluoro-substituted aromatic amides with alkynes results in C-F/N-H annulation to give 1(2H)-isoquinolinones. A key to the success of the reaction is the use of KO t Bu or even weak base, such as Cs2CO3. The reaction proceeds in the absence of a ligand and under mild reaction conditions (40-60 °C). DFT calculations suggest that the pathway for this Ni-catalyzed C-F/N-H annulation involves N-H deprotonation, oxidative addition of a C-F bond, migratory insertion of an alkyne, and reductive elimination to form 1(2H)-isoquinolinone derivatives.Thermoelectric conversion of low temperature, delocalized, and abundant thermal sources is crucial for the development of the Internet of Things (IoT) and/or a carbon-free society. find more Thermocells are of great interest in thermoelectric conversion of low-temperature heat due to the low cost and flexibility of components. However, significant improvement of the conversion efficiency is required for the practical use of the cells. Here, we report thermo-electrochemical cells driven by volume phase transition (VPT) of hydrogel nanoparticles (NPs). Entropically driven VPT of poly(N-isopropylacrylamide) NPs containing carboxylic acids and amines generates a pH gradient of up to 0.049 and -0.053 pH K-1, respectively, around physiological temperature. The pH gradient triggers the proton-coupled electron transfer (PCET) reactions of quinhydrone on the electrodes, resulting in the highly efficient thermoelectric conversion with a Seebeck coefficient (Se) of -6.7 and +6.1 mV K-1. Thermocells driven by phase transition of hydrogels provide a nontoxic, flexible, and inexpensive charger that harvests carbon-free energy from abundant energy sources such as solar, body and waste heat.A new strategy to create highly redox-responsive H-bond dimers based on proton-coupled electron transfer is proposed that capitalizes on the importance of secondary H-bonds in determining overall binding strength in H-bond dimers. Electron transfer induced proton transfer across a H-bond can be used to significantly strengthen the overall binding by both creating strong ionic H-bonds and changing the secondary H-bonds from unfavorable to favorable. The viability and potency of this approach are demonstrated with an electroactive DAD (A = H-acceptor, D = H-donor) array, H(MQ+)H, paired with an electroinactive ADA array, O(NH)O. NMR titration of H(MQ+)H with O(NH)O in 0.1 M NBu4PF6/CD2Cl2 gives a Kassoc of 500 M-1, typical of DAD-ADA dimers. However, upon two-electron reduction in 0.1 M NBu4PF6/CH2Cl2, cyclic voltammetry studies indicate a 1.8 × 105 increase in binding strength, corresponding to a very large Kassoc of 9 × 107 M-1. The latter value is typical of DDD-AAA H-bond dimers, consistent with proton transfer across the central H-bond upon reduction.Designing new materials for the effective detoxification of chemical warfare agents (CWAs) is of current interest given the recent use of CWAs. Although halogenated boron-dipyrromethene derivatives (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene or BDP or BODIPY) at the 2 and 6 positions have been extensively explored as efficient photosensitizers for generating singlet oxygen (1O2) in homogeneous media, their utilization in the design of porous organic polymers (POPs) has remained elusive due to the difficulty of controlling polymerization processes through cross-coupling synthesis pathways. Our approach to overcome these difficulties and prepare halogenated BODIPY-based porous organic polymers (X-BDP-POP where X = Br or I) represents an attractive alternative through post-synthesis modification (PSM) of the parent hydrogenated polymer. Upon synthesis of both the parent polymer, H-BDP-POP, and its post-synthetically modified derivatives, Br-BDP-POP and I-BDP-POP, the BET surface areas of all POPs have been measured and found to be 640, 430, and 400 m2·g-1, respectively.