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A gold(I)‐catalyzed enantioselective dearomatization is achieved via metal‐chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl‐2‐ylphosphines is developed to allow rapid access to these ligands, which in turn facilitate the application of this chemistry to a broad substrate scope including 1‐naphthols, 2‐naphthols, and phenols. Enantiomeric excesses up to 98 % are achieved via selective acceleration of one enantiomer formation enabled by hydrogen bonding between substrate and ligand remote basic group. DFT calculations lend support to the cooperative catalysis and substantiate the reaction stereochemical outcomes.

 

Reaction of [Ni(1,5-cod) 2 ] (30 equiv.) with PEt 3 (46 equiv.) and S 8 (1.9 equiv.) in toluene, followed by heating at 115 °C for 16 h, results in the formation of the atomically precise nanocluster (APNC), [Ni 30 S 16 (PEt 3 ) 11 ] (1), in 14% isolated yield. Complex 1 represents the largest open-shell Ni APNC yet isolated. In the solid state, 1 features a compact “metal-like” core indicative of a high degree of Ni–Ni bonding. Additionally, SQUID magnetometry suggests that 1 possesses a manifold of closely-spaced electronic states near the HOMO–LUMO gap. In situ monitoring by ESI-MS and 31 P{ 1 H} NMR spectroscopy reveal that 1 forms via the intermediacy of smaller APNCs, including [Ni 8 S 5 (PEt 3 ) 7 ] and [Ni 26 S 14 (PEt 3 ) 10 ] (2). The latter APNC was also characterized by X-ray crystallography and features a nearly identical core structure to that found in 1. This work demonstrates that large APNCs with a high degree of metal–metal bonding are isolable for nickel, and not just the noble metals. 

We investigate the influence of the host matrix on the photothermally driven actuation performance of negatively photochromic, donor−acceptor Stenhouse adduct (DASA)-based polymers. Using a modular Diels−Alder “click” platform, we designed polymeric materials with varying DASA incorporation and investigated the relationships between the material composition and the resulting physical, mechanical, and photoswitching properties. We demonstrate that increasing the DASA concentration in polymer conjugates has a dramatic effect on the material’s physical and mechanical properties, such as the glass transition temperature (Tg) and elastic modulus, as well as the photoswitching properties, which are found to be highly dependent on Tg. We establish using a simple photoresponsive bilayer that actuation performance is controlled by the bilayer stiffness rather than the photochrome incorporation of DASA. Finally, we report and compare the light-induced property changes in Tg and the elastic modulus between the materials comprising the open or closed forms of DASAs. Our results demonstrate the importance of designing a material that is stiff enough to provide the mechanical strength required for actuation under load, but soft enough to reversibly switch at the operational temperature and provide key considerations for the development of application-geared photoswitchable materials.