Concerns about the toxicity and instability of lead-halide perovskites have driven a recent surge in research toward alternative lead-free perovskite materials, including lead-free double perovskites with the elpasolite structure and visible bandgaps. Synthetic approaches to this class of materials remain limited, however, and no examples of heterometallic elpasolites as nanomaterials have been reported. Here, we report the synthesis and characterization of colloidal nanocrystals of CsAgBiX (X = Cl, Br) elpasolites using a hot-injection approach. We further show that postsynthetic modification through anion exchange and cation extraction can be used to convert these nanocrystals to new materials including CsAgBiI, which was previously unknown experimentally. Nanocrystals of CsAgBiI, synthesized via a novel anion-exchange protocol using trimethylsilyl iodide, have strong absorption throughout the visible region, confirming theoretical predictions that this material could be a promising photovoltaic absorber. The synthetic methodologies presented here are expected to be broadly generalizable. This work demonstrates that nanocrystal ion-exchange reactivity can be used to discover and develop new lead-free halide perovskite materials that may be difficult or impossible to access through direct synthesis.

While recent spectroscopic studies have established the presence of an interstitial carbon atom at the center of the iron-molybdenum cofactor (FeMoco) of MoFe-nitrogenase, its role is unknown. We have pursued Fe-N2 model chemistry to explore a hypothesis whereby this C-atom (previously denoted as a light X-atom) may provide a flexible trans interaction with an Fe center to expose an Fe-N2 binding site. In this context, we now report on Fe complexes of a new tris(phosphino)alkyl (CPiPr3) ligand featuring an axial carbon donor. It is established that the iron center in this scaffold binds dinitrogen trans to the Calkyl-atom anchor in three distinct and structurally characterized oxidation states. Fe-Calkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-Calkyl interaction. The anionic (CPiPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CPiPr3)Fe-N2SiR3. (CPiPr3)FeN2- also functions as a modest catalyst for the reduction of N2 to NH3 when supplied with electrons and protons at -78 °C under 1 atm N2 (4.6 equiv NH3/Fe).

Ullman Upgrade Precious metals may dominate contemporary catalysis, but the early development of synthetic organic chemistry relied on more abundant elements—a strategy that chemists are returning to now for the sake of sustainability. Copper-mediated coupling of aryl halides with amines was reported by Ullman more than a century ago and remains in use today for the synthesis of certain organic compounds. However, the reaction generally requires high temperature to proceed efficiently. Creutz et al. (p. 647 ) have developed a photochemical variant that uses copper and reacts at room temperature or below, apparently by a radical mechanism.

No abstract

A two-step solution-deposition method for preparing ytterbium-doped (Yb3+) CsPb­(Cl1–x Br x )3 perovskite thin films is described. Yb3+-doped CsPb­(Cl1–x Br x )3 films are made that exhibit intense near-infrared photoluminescence with extremely high quantum yields reaching over 190%, stemming from efficient quantum cutting that generates two emitted near-infrared photons for each absorbed visible photon. The near-infrared Yb3+ f–f photoluminescence is largely independent of the anion content (x) in CsPb­(Cl1–x Br x )3 films with energy gaps above the quantum-cutting threshold of twice the Yb3+ f–f transition energy, but it decreases abruptly when the perovskite energy gap becomes too small to generate two Yb3+ excitations. Excitation power dependence measurements show facile saturation of the Yb3+ luminescence intensity, identifying a major challenge for future solar applications of these materials.