A trinucleating cyclophane bearing three β-diketimine arms, and the corresponding iron(II) and manganese(II) complexes have been synthesized and characterized. The three metal ions are oriented towards the internal void space, and are coordinated by a N2Br2 donor set, in which a unique combination of μ(3), μ, and terminal coordination modes are observed for the halide donors.

Extended metal atom chain (EMAC) complexes of first-row transition metals with metal−metal bonds have the potential to elicit unique magnetic properties and reactivities. Until now, the library of EMAC complexes with late-first-row transition metals was incomplete because of the omission of a triiron species with Fe−Fe bonding. Herein we report the synthesis and preliminary investigation of the first linear, triiron(II) complex containing close Fe−Fe interactions. The complex is supported by three dianionic 2,6-bis[(trimethylsilyl)amido]pyridine ligands (L), with an overall composition of Fe 3 L 3 , and pseudohelical ligand coordination stabilizing the local trigonal-planar geometry at each iron. Fe 3 L 3 was characterized by X-ray diffraction, 1 H NMR, cyclic voltammetry, electronic absorption, and Mossbauer spectroscopies. Evans method analysis indicated a large uncompensated spin and an S = 6 ground state, suggesting ferromagnetic coupling in the triiron chain, likely due to direct exchange.

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While ionic liquids have proved to be versatile materials for a wide spectrum of applications, e.g., energy, materials, and medicine, several challenges remain concerning the rational design of novel materials. In light of this, a series of four triphenylphosphonium-based ionic liquids have been synthesized for the first time. These compounds exhibit high thermal stability with decomposition temperatures up to 450 °C. Their solid-state structures are characterized by single-crystal X-ray diffraction and the intermolecular interactions rigorously analyzed via Hirshfeld surface analysis. It was found that the unique geometries of the anions used in the study form distinct interactions with the cations. The interactions in the crystalline state are correlated with the thermal properties of the four ionic liquids to rationalize the melting points and phase transitions for each compound. The observed arrangements of the alkyl chains on the cations are investigated computationally to gain an understanding of how rotational freedom may impact the thermal properties of the compounds. By intention, each IL reported in this work offers a unique property profile and contributes to the ever-growing ionic liquid catalog.

A series of tri- and dimetallic metal complexes of pyridine dicarboxamide cryptates are reported in which changes to the base and metal source result in diverse structure types. Addition of strong bases, such as KH or KN(SiMe3)2, followed by divalent metal halides allows direct access to trinuclear complexes in which each metal center is coordinated by a dianionic N,N,N-chelate of each arm. These complexes bind a guest K(+) cation within the central cavity in a trigonal planar coordination environment. Minor changes to the solvent and equivalents of base used in the syntheses of the triiron(II) and tricobalt(II) complexes affords two trinuclear clusters with atypical O,N,O-coordination by each pyridine dicarboxamide arm; the amide carbonyl O atoms are oriented toward the interior of the cavity to coordinate to each metal center. Finally, varying the base enables the selective synthesis of dinuclear nickel(II) and copper(II) complexes in which one pyridine dicarboxamide arm remains protonated. These amide protons are at one end of a hydrogen bonding network that extends throughout the internal cavity and terminates at a metal bound hydroxide, carbonate, or bicarbonate donor. In the dinickel complex, the bicarbonate cannot be liberated as CO2 either thermally or upon sparging with N2, which differs from previously reported monometallic complexes. The carbonate or bicarbonate ligands likely arise from sequestration of atmospheric CO2 based on the observed reaction of the di(hydroxonickel) analog.