The linear trinuclear complex cation [Fe3(DpyF)4]2+ was prepared as [Fe3(DpyF)4](BF4)2·2CH3CN. With large Fe-Fe distances of 2.78 Å, this complex demonstrates intramolecular ferromagnetic coupling between the anisotropic FeII centers (J/kB = +20.9(5) K) giving an ST = 6 ground state and exhibits single-molecule magnet properties.

In this work we provide direct experimental evidence on the correlation of remote interactions between a newly synthesized Mn-I-complex (1) and different alkali cations with redox potential tuning. Furthermore we report the electrochemical behavior of 1 towards carbon dioxide, including the effects of added alkali salts using cyclic voltammetry.

Linear polynuclear paddlewheel complexes-extended atom chains or metal strings-have provided attractive models for the study of metal-metal bonding, magnetism and conductivity since their discovery in the 1990s [1]. Their helicoidal chirality, arising from mutual steric hindrance of the 3-pyridyl protons, resulting in the twisting of the equatorial ligand around the axis (see figure), has been less studied. Nonetheless, in one of the few examples of chiral resolution, the obtained enantiomers of a trinickel complex showed a remarkably high specific rotation of 5000 deg•mL•g −1 •dm −1 [2], motivating us to seek a general technique for the chiral resolution of such racemates. We have developed a procedure based on anion exchange for the chiral resolution of [M3(dpa)4] 2+ salts (M = Co(II) or Ni(II), Hdpa = 2,2'-dipyridylamine). Homochiral arsenyl tartrate (AsT) salts promoted the selective crystallization of [-M3(dpa)4(MeCN)2](NBu4)2[-AsT]2, or [-M3(dpa)4(MeCN)2](NBu4)2[-AsT]2 in the P4212 space group. The enantiopure compounds demonstrated surprisingly large optical activities using UV-vis, Raman and infrared spectroscopy in solution and, for the cobalt derivatives, in the X-ray range at the Co K-edge in single crystals. An intense X-ray linear dichroism was observed in the orthoaxial crystal orientation, whereas it vanished in the axial confirmation, while the angular dependence of the circular dichroism spectra followed the expected (3cos 2 − 1) function, thus spectroscopically confirming the D4 crystal symmetry. X-ray magnetic circular dichroism and X-ray magnetochiral dichroism signals at the Co K-edge were not detected, likely due to a strongly delocalized spin density on the metal-metal bonded tricobalt core. Nevertheless, these results establish that chiral polynuclear paddlewheel complexes can be cleanly resolved using selective crystallization and demonstrate considerable optical activity in the infrared, UV-vis and X-ray energy ranges, thus potentially offering future perspectives in non-linear optics and asymmetric synthesis [3].

Trinuclear cobalt paddlewheel complexes, [Co3(dpa)4X2] (dpa = the anion of 2,2'-dipyridylamine, X = Cl-, Br-, -NCS-, -CN-, (NC)2N-), 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 (T1/2) 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) T1/2 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 T1/2 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.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A boratriazine ligand, which incorporates attractive features from both bodipy and terpy, has been used to synthesize [Fe2II(μ1,1-N3)2(Py2F2BTA)2(N3)2] (1) and [Co2II(μ1,1-N3)2(Py2F2BTA)2(N3)2] (2). Both 1 and 2 feature a double end-on azido bridging motif, which promotes ferromagnetic interactions between the metal centres. Indeed, 1 represents the first report of a dinuclear FeII complex with this bridging mode exhibiting J = 5.7(9) cm-1 and D = -6.0(4) cm-1, while the isostructural Co analogue shows J = 7.1(9) cm-1 and D = 17.3(9) cm-1.

Enantiopure single crystals of extended metal atom chains display exceptionally large optical X-ray dichroisms at the Co K-edge.