Synthesis of Ionizable Calix[4]arenes for Chelation of Selected Divalent Cations.

Two sets of functionalised calix[4]arenes, either with a 1,3-crown ether bridge or with an open-chain oligo ether moiety in 1,3-position were prepared and further equipped with additional deprotonisable sulfonamide groups to establish chelating systems for selected cations Sr2+, Ba2+, and Pb2+ ions. To improve the complexation behaviour towards these cations, calix[4]arenes with oligo ether groups and modified crowns of different sizes were synthesized. Association constants were determined by UV/Vis titration in acetonitrile using the respective perchlorate salts and logK values between 3.2 and 8.0 were obtained. These findings were supported by the calculation of the binding energies exemplarily for selected complexes with Ba2+.

Mechanistically Driven Control over Cubane Oxo Cluster Catalysts.

Predictive and mechanistically driven access to polynuclear oxo clusters and related materials remains a grand challenge of inorganic chemistry. We here introduce a novel strategy for synthetic control over highly sought-after transition metal {M4O4} cubanes. They attract interest as molecular water oxidation catalysts that combine features of both heterogeneous oxide catalysts and nature's cuboidal {CaMn4O5} center of photosystem II. For the first time, we demonstrate the outstanding structure-directing effect of straightforward inorganic counteranions in solution on the self-assembly of oxo clusters. We introduce a selective counteranion toolbox for the controlled assembly of di(2-pyridyl) ketone (dpk) with M(OAc)2 (M = Co, Ni) precursors into different cubane types. Perchlorate anions provide selective access to type 2 cubanes with the characteristic {H2O-M2(OR)2-OH2} edge-site, such as [Co4(dpy-C{OH}O)4(OAc)2(H2O)2](ClO4)2. Type 1 cubanes with separated polar faces [Co4(dpy-C{OH}O)4(L2)4] n+ (L2 = OAc, Cl, or OAc and H2O) can be tuned with a wide range of other counteranions. The combination of these counteranion sets with Ni(OAc)2 as precursor selectively produces type 2 Co/Ni-mixed or {Ni4O4} cubanes. Systematic mechanistic experiments in combination with computational studies provide strong evidence for type 2 cubane formation through reaction of the key dimeric building block [M2(dpy-C{OH}O)2(H2O)4]2+ with monomers, such as [Co(dpy-C{OH}O)(OAc)(H2O)3]. Furthermore, both experiments and DFT calculations support an energetically favorable type 1 cubane formation pathway via direct head-to-head combination of two [Co2(dpy-C{OH}O)2(OAc)2(H2O)2] dimers. Finally, the visible-light-driven water oxidation activity of type 1 and 2 cubanes with tuned ligand environments was assessed. We pave the way to efficient design concepts in coordination chemistry through ionic control over cluster assembly pathways. Our comprehensive strategy demonstrates how retrosynthetic analyses can be implemented with readily available assembly directing counteranions to provide rapid access to tuned molecular materials.

A Redox-Induced Spin-State Cascade in a Mixed-Valent Fe3 (µ3 -O) Triangle.

One-electron reduction of a pyrazolate-bridged triangular Fe3 (µ3 -O) core induces a cascade wherein all three metal centers switch from high-spin Fe3+ to low-spin Fe2.66+ . This hypothesis is supported by spectroscopic data (1 H-NMR, UV-vis-NIR, infra-red, 57 Fe-Mössbauer, EPR), X-ray crystallographic characterization of the cluster in both oxidation states and also density functional theory. The reduction induces substantial contraction in all bond lengths around the metal centers, along with diagnostic shifts in the spectroscopic parameters. This is, to the best of our knowledge, the first example of a one-electron redox event causing concerted change in multiple iron centers.

Synthesis, structural studies and computational evaluation of cyclophanes incorporating imidazole-2-selones.

We report new cyclophanes containing imidazole-2-selone groups linked by xylylene rings. A set of imidazole-2-selone cyclophanes is synthesized by reaction corresponding to imidazolium cyclophanes with selenium in the presence of K2CO3. The structural behavior of the new imidazole-2-selone cyclophanes was determined by 1H and 13C NMR spectra and X-ray diffraction studies. Cyclophanes incorporating o-xylylene or mesitylene-m-cyclophane linked by selone groups were mutually syn in both the solid state and solution, and the cyclophanes showed a conformation similar to the cone conformation of calix[4]arenes. Cyclophanes incorporating p-xylylene or m-xylylene linked by selone groups showed two conformations in the solution: one mutually syn and the other mutually anti. There was no interconversion for both conformations observed on the NMR timescale. In the solid state, three conformations were detected for the p-xylylene-linked cyclophane: one is mutually syn and the other two are mutually anti and partial cone conformations. In the m-xylylene-linked case, only anti-conformation was characterized in the solid state. A density functional analysis was conducted to interpret the stability of the studied compounds and shed light on their origin. The energy preference analysis is in consistent agreement with the observed geometries and their co-existence.

Site preferences in hetero-metallic [Fe9-xNix] clusters: a combined crystallographic, spectroscopic and theoretical analysis.

The reaction of mixtures of Fe(O2CMe)2·2H2O and Ni(O2CMe)2·4H2O of various compositions with di-2-pyridyl ketone (py2CO, dpk) in MeCN under an inert atmosphere afforded a family of hetero-metallic enneanuclear clusters with general formula [Fe9-xNix(µ4-OH)2(O2CMe)8(py2CO2)4] (2, x = 1.00; 3: x = 6.02; 4, x = 7.46; 5, x = 7.81). Clusters 2-5 are isomorphous to the homo-metallic [Fe9] cluster (1) previously reported by some of us, and also isostructural to the known homo-metallic [Ni9] cluster. All four clusters contain a central MII ion in an unusual 8-coordinate site and eight peripheral MII ions in distorted octahedral environments. The distribution of FeII and NiII ions over these two distinct coordination sites in 2-5 can be established through a combination of X-ray fluorescence and Mössbauer spectroscopies, which show that FeII preferentially occupies the unique 8-coordinate metal site while NiII accumulates in the octahedral holes. Density functional theory indicates that the distribution of ions across the two sites arises not from any intrinsic preference of the FeII ions for the 8-coordinate sites, but rather because of the large ligand field stabilization energy available to NiII in octahedral coordination.

A trigonal prismatic Cu6-pyrazolato complex containing a µ6-F ligand.

The encapsulation of a fluoride ion in a trigonal prismatic CuII6-pyrazolato cage results in a small expansion of the Cu6-host. The structural, electronic and magnetic features of the Cu6-complex, containing an endohedral fluoride in the rare µ6-F coordination mode, are compared with those of the parent complex with a vacant Cu6-cage.