An isostructural series of Np­(V) MOFs with shp-topology were synthesized and characterized. X-ray diffraction data revealed an unusual wheel-shaped node of 18 neptunyl polyhedra stabilized in the framework. Strong distortion in local coordination of the neptunium atoms is evidenced by Np–Oyl bond lengths that lie outside the typical range for Np­(V). The structure was further interrogated by Raman spectroscopy and density functional theory calculations to assign the vibrational modes.

Olefin metathesis is a broadly employed reaction with applications that range from fine chemicals to materials and petrochemicals. The design and investigation of olefin metathesis catalysts have been ongoing for over half a century, with advancements made in terms of activity, stability, and selectivity. Immobilization of organometallic complexes onto solid supports such as silica or alumina is a promising strategy for catalyst heterogenization, often resulting in increased activity and stability. Consequently, a broad range of early transition metal catalysts bearing alkyl, oxide/alkoxide, and amide ligands have been grafted onto silica and their reactivities investigated. Herein, we report a series of silica-supported tungsten and molybdenum dimers (X 3 MMX 3 , where M = W and Mo; X = neopentyl, tert-butoxide, and dimethyl amide) and their reactivities toward catalytic olefin metathesis. Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR), diffuse reflectance infrared Fourier transform (DRIFT), UV resonance Raman, and X-ray absorption (XAS) spectroscopies suggest that upon heterogenization the dimers bind to the surface in a monopodal fashion, with the MM triple bond remaining intact. These structural assignments were further corroborated by density functional theory (DFT) calculations. While the homogeneous dimer counterparts are inert, the supported low-valent alkyl W and Mo dimers become active for the disproportionative self-metathesis of propylene to ethylene and butenes and 4-nonene to 4-octene and 5-decene under mild conditions. The lack of activity observed for the free and supported tert-butoxide and dimethyl amide dimers likely suggests that the neopentyl groups are necessary for the formation of a putative alkylidene active species. The difference in reactivity between the free and supported dimers could be explained either by the lowering of the activation barrier of the complex through the electronic effects of the surface or by site isolation of catalytically relevant reactive intermediates.

Experimental and quantum mechanical characterization of an oxygen-bridged plutonium(IV) dimer Authors: Debmalya Ray; Jing Xie; Jacob White; Ginger E. Sigmon; Laura Gagliardi; Amy E. Hixon This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

We investigated the magnetic and optical properties of ͑2 , 3-dmpyH͒ 2 CuBr 4 , an unusual antiferromagnetic quantum spin ladder with strong rail interactions that can be saturated in a 30 T field. This transition drives a field-induced color change, a dramatic example of charge-spin coupling in a molecular material. Spin-density calculations reveal that electronic structure is sensitive to the magnetic state because magnetic orbital character depends on the spin arrangement between adjacent CuBr 4 2− chromophores. This finding suggests that molecular architecture and the magnetic arrangement between molecular units might be used to control magnetochromism.