Intermolecular Proton-Coupled Electron Transfer Reactivity from a Persistent Charge-Transfer State for Reductive Photoelectrocatalysis.

Interest in applying proton-coupled electron transfer (PCET) reagents in reductive electro- and photocatalysis requires strategies that mitigate the competing hydrogen evolution reaction. Photoexcitation of a PCET donor to a charge-separated state (CSS) can produce a powerful H-atom donor capable of being electrochemically recycled at a comparatively anodic potential corresponding to its ground state. However, the challenge is designing a mediator with a sufficiently long-lived excited state for bimolecular reactivity.

Low-Valent Metal Ions as MOF Pillars: A New Route Toward Stable and Multifunctional MOFs.

PCM-102 is a new organophosphine metal-organic framework (MOF) featuring diphosphine pockets that consist of pairs of offset oriented P(III) donors. Postsynthetic addition of M(I) salts (M = Cu, Ag, Au) to PCM-102 induces single-crystal to single-crystal transformations and the formation of -[PM] solid-state complexes (where P = framework-based triarylphosphines). While the unmetalated PCM-102 has low porosity, the addition of secondary Lewis acids to install rigid P-M-P pillars is shown to dramatically increase both stability and selective gas uptake properties, with N Brunauer-Emmett-Teller surface areas >1500 m g.

Hierarchical nanosheets built from superatomic clusters: properties, exfoliation and single-crystal-to-single-crystal intercalation.

Tuning the properties of atomic crystals in the two-dimensional (2D) limit is synthetically challenging, but critical to unlock their potential in fundamental research and nanotechnology alike. 2D crystals assembled using superatomic blocks could provide a route to encrypt desirable functionality, yet strategies to link the inorganic blocks together in predetermined dimensionality or symmetry are scarce. Here, we describe the synthesis of anisotropic van der Waals crystalline frameworks using the designer superatomic nanocluster Co(py)CoSeL (py = pyridine, L = PhPN(Tol)), and ditopic linkers.