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Reaction of CoCO 3 with α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid (H 2 esp) in EtOH forms the paddlewheel-type dimer Co 2 (esp) 2 (EtOH) 2 , which hydrolyzes in MeCN to give a bowl-shaped heptacobalt coordination cluster complex; both compounds display antiferromagnetic interactions between high-spin Co( ii ) ions.
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A novel cluster capping strategy is employed to leverage the structural diversity of metal–organic cages toward the isolation of porous cages.
One of the main challenges with using flat panel photobioreactors for algal growth is uneven mixing and settling of cells in corners, especially when bubbling is the only method used for mixing. Here, in order to improve mixing in our flat panel reactor, we designed a custom paddlewheel. Paddlewheels are frequently used in outdoor algae raceway ponds to improve mixing and we are taking advantage of the same principle for mixing in the reactor. The paddlewheel is easily integrated into our PSI FMT150 1‐L flat panel photobioreactor and is printed on a 3D printer using high temperature poly lactic acid (HT‐PLA). With the inclusion of an annealing step, the paddlewheel is autoclavable. Addition of the paddlewheel in the reactor minimized cell settling and improved algal growth, as evidenced by a nearly 40% increase in oxygen production rates. Nutrient dispersion and utilization in the culture was also improved as evidenced by a corresponding 38% decrease in CO 2 concentration. The paddlewheel device presented here is a cost‐effective method for improving algal growth in a flat panel photobioreactor.
Copper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal–organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu₂(O₂C-)₄], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu₃O(N 4–x (CH) x C-)₃] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1.
Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic conductivity remain poorly understood. Here, ab initio molecular dynamics is used to characterize migration processes in the prototype glass, 75Li2S–25P2S5. Lithium migration occurs via a mechanism that combines concerted motion of lithium ions with large, quasi-permanent reorientations of PS4 3- anions. This latter effect, known as the ‘paddlewheel’ mechanism, is typically observed in high temperature crystalline polymorphs. In contrast to the behavior of crystalline materials, in the glass paddlewheel dynamics contribute to Lithium-ion mobility at room temperature. Paddlewheel contributions are confirmed by characterizing spatial, temporal, vibrational, and energetic correlations with Lithium motion. Furthermore, the dynamics in the glass differ from those in the stable crystalline analogue, γ-Li3PS4, where anion reorientations are negligible and ion mobility is reduced. These data imply that glasses containing complex anions, and in which covalent network formation is minimized, may exhibit paddlewheel dynamics at low temperature. Consequently, these systems may be fertile ground in the search for new solid electrolytes.
Since the 1980s, the paddlewheel effect has been suggested as a mechanism to boost lithium-ion diffusion in inorganic materials via the rotation of rotor-like anion groups. However, it remains unclear whether the paddlewheel effect, defined as large-angle anion group rotations assisting Li hopping, indeed exists; furthermore, the physical mechanism by which the anion-group dynamics affect lithium-ion diffusion has not yet been established. In this work, we differentiate various types of rotational motions of anion groups and develop quaternion-based algorithms to detect, quantify, and relate them to lithium-ion motion in ab initio molecular dynamics simulations. Our analysis demonstrates that, in fact, the paddlewheel effect, where an anion group makes a large angle rotation to assist a lithium-ion hop, does not exist and thus is not responsible for the fast lithium-ion diffusion in superionic conductors, as historically claimed. Instead, we find that materials with topologically isolated anion groups can enhance lithium-ion diffusivity via a more classic nondynamic soft-cradle mechanism, where the anion groups tilt to provide optimal coordination to a lithium ion throughout the hopping process to lower the migration barrier. This anion-group disorder is static in nature, rather than dynamic and can explain most of the experimental observations. Our work substantiates the nonexistence of the long-debated paddlewheel effect and clarifies any correlation that may exist between anion-group rotations and fast ionic diffusion in inorganic materials.
We appreciate the engagement from Smith and Siegel on the topic of the “paddlewheel effect” and are pleased to see alignment regarding the absence of a paddlewheel effect, in which large-angle anion-group rotations directly propel lithium hops. In our paper, we clearly state the ambiguity surrounding the term “paddlewheel” to describe lithium transport. We believe that science is not well served by this vague term or its regular redefinition which is why we distinguish three types of anion-group rotation events: large-angle rotations (n-fold rotation returning to a rotationally invariant configuration), librations (e.g., rotational vibrations), and static changes of orientation in response to the change of Li occupancy. Here, we directly evaluate the spatial and temporal correlation between such polyanion rotations and Li hops.
Abstract The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOF NU‐1700 , assembled from U 4+ ‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U 4+ ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.
Abstract The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOF NU‐1700 , assembled from U 4+ ‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U 4+ ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.
Trinuclear cobalt paddlewheel complexes, [Co 3 (dpa) 4 X 2 ] (dpa = the anion of 2,2'-dipyridylamine, X = Cl–, Br–, –NCS–, –CN–, (NC) 2 N–), are known to demonstrate a thermally-induced spin-crossover (SCO). Despite a wealth of structural and magnetic information about such complexes, the role of the axial ligand on the characteristic SCO temperature (T 1/2 ) remains ambiguous. The situation is complicated by the observation that the solid state geometry of the complexes, symmetric or unsymmetric, with respect to the central cobalt ion, also appears to influence the SCO behavior. In order to seek trends in the relationship between the nature of the axial ligand, geometry and magnetic properties, we have prepared the first examples of tricobalt paddlewheel complexes with axial fluorido and iodido ligands, as well as two new chlorido and bromido solvates. Their SCO properties are discussed in the context of an examination of previously reported chlorido and bromido adducts. The main conclusions are: (1) T 1/2 values follow the trend I– < Br– ≈ Cl– < F–; (2) while the molecular geometry is predominantly guided by crystal packing for the Cl–, Br– and I– derivatives, the presence of an axial fluoride may favor a more symmetric core; (3) the magnetic characterization of a second example of an unsymmetric complex supports the observation that they display dramatically lower T 1/2 values than their symmetric analogues; and (4) SCO in crystallographically symmetric compounds apparently occurs without loss of molecular or crystallographic symmetry, while a gradual geometric transformation linking the temperature dependence of quasi-symmetric to unsymmetric in crystallographically unconstrained compounds was found.
Although paddlewheel-based structures are common among permanently porous metal–organic materials, suitable strategies for the isolation of metal node-terminated, capped paddlewheel-based cage structures remain limited. We explored the use of chelating dicarboxylate ligand derivates (esp) for the isolation of trimesate-linked cages, Mo 12 (btc) 4 (esp) 6 , that are structural analogs of the small octahedral pore of HKUST-1. The porosity of these novel cages is appreciably higher than that of previously reported structures of this type. We also demonstrate that pillaring the isolated cage with DABCO generated an amorphous polymer that featured exceptional thermal stability and enhanced porosity.
The use of electrolyte additives at millimolar loadings to control the surface chemistry of lithium metal anodes (LMAs) is a leading strategy to improve lithium metal batteries and promote electrosynthetic reactions. Whereas previous studies employed either inorganic or organic additives, in this study, we report the first organometallic additive, Mo 2 (mea) 4 [1, mea = 2-(2-methoxyethoxy)acetate], a dimolybdenum paddlewheel complex that is stable under Li plating conditions and features cation binding sites in the second coordination sphere that promote reversible Li + coordination. Binding of Li + ions to 1 induces immobilization of cationically charged aggregates (or products thereof) into the solid electrolyte interphase (SEI), imparting multiple beneficial functions. The modified SEI was found to protect the LMA against parasitic side reactions, produce modest but measurable improvements to Li plating properties (e.g., overpotential, surface structure, and Coulombic efficiency), and improve interfacial charge transport properties. Furthermore, the most notable benefit to battery cycling performance appears in calendar aging tests, which show that the presence of the additive protects the LMA from parasitic side reactions that would otherwise decrease overall cell cycling efficiency over time. Collectively, these data disclose a tactic for designing electrolyte additives using principles of organometallic synthesis.
Satellite surface and particle interaction measurements in upper atmosphere using paddlewheel satellites
Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2 L 4 F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp – ); 2, L = diphenyl formamidinate (dpf – )) were prepared from the solid-state melt reactions (SSMRs) between (NH 4 ) 2 [Re 2 F 8 ]·2H 2 O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2 (hpp) 4 F 2 ]PF 6 (3) was prepared from the one-electron oxidation of Re 2 (hpp) 4 F 2 with [Cp 2 Fe]PF 6 . Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoes two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2 (hpp) 4 F 2 (1) is more easily oxidized than its chloro and bromo analogues.
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