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The Paternò–Büchi reaction is the [2+2] photocycloaddition of a carbonyl with an alkene to afford oxetane products. Enantioselective catalysis of this classical photoreaction, however, has proven to be a long-standing challenge. Many of the best-developed strategies for asymmetric photochemistry are not suitable to address this problem because the interaction of carbonyls with Brønsted or Lewis acidic catalysts can alter the electronic structure of their excited state and divert their reactivity towards alternate photoproducts. We show herein that an alternative triplet rebound strategy enables the stereocontrolled reaction of an excited-state carbonyl compound in its native, unbound state. These studies have resulted in the development of the first highly enantioselective catalytic Paternò–Büchi reaction, cata-lyzed by a novel hydrogen-bonding chiral Ir photocatalyst. 

Vibrational fingerprints and combination bands are a direct measure of couplings that control molecular properties. However, most combination bands possess small transition dipoles. Here we use multiple, ultrafast coherent infrared pulses to resolve vibrational coupling between CH3CN fingerprint modes at 918 and 1039 cm(-1) and combination bands in the 2750-6100 cm(-1 )region via doubly vibrationally enhanced (DOVE) coherent multidimensional spectroscopy (CMDS). This approach provides a direct probe of vibrational coupling between fingerprint modes and near-infrared combination bands of large and small transition dipoles in a molecular system over a large frequency range. 

By using tunable lasers to entangle rotational, vibrational, and electronic states, researchers are learning more about molecules and their properties than from previous methods. 

Amorphous magnetic alloys with large perpendicular magnetic anisotropy (PMA) have emerged as a suitable material choice for spintronic memory and high-frequency non-reciprocal devices on-chip. Unlike ferromagnets, ferrimagnets offer faster switching dynamics, lower net saturation magnetization, minimal stray field and a lower net angular momentum. Ferrimagnetic thin films of Gd x Co 1− x sputter deposited as heterostructures of Ta/Pt/Gd x Co 1− x (t)/Pt on Si/SiO 2 have bulk-like PMA for thicknesses of 5–12 nm and room-temperature magnetic compensation for x = 28–32%. Preferential oxygenation of GdCo has been found to increase the effective anisotropy energy density by an order of magnitude and produce near-ideal remanence ratios. X-ray photoelectron spectroscopy accurately quantifies the metal-oxidation ratio, which shows that an oxygen-rich and Co-deficient stoichiometry (Gd 21 Co 28 O 51 ) likely weakens the ferromagnetic exchange interaction between Co–Co and contributes additional antiferromagnetic exchange through superexchange-like interactions between Gd and Co via O, resulting in a stronger out-of-plane magnetization. Even greater PMA and giant-anisotropy field of 11 kOe are achieved in super-lattices of the Gd 21 Co 28 O 51 heterostructure. The combination of ferrimagnetic ordering in amorphous Gd x Co 1− x and its affordance of pathways for engineering large PMA will enable the design of integrated high-frequency devices beyond 30 GHz and ultrafast energy efficient memory devices with switching speeds down to tens of picoseconds.