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A Co /porphyrinate-based macrocycle in the presence of a 3,5-diphenylpyridine axial ligand functions as an endotopic ligand to direct the assembly of [2]rotaxanes from diazo and styrene half-threads, by radical-carbene-transfer reactions, in excellent 95 % yield. The method reported herein applies the active-metal-template strategy to include radical-type activation of ligands by the metal-template ion during the organometallic process which ultimately yields the mechanical bond. A careful quantitative analysis of the product distribution afforded from the rotaxane self-assembly reaction shows that the Co /porphyrinate subunit is still active after formation of the mechanical bond and, upon coordination of an additional diazo half-thread derivative, promotes a novel intercomponent C-H insertion reaction to yield a new rotaxane-like species. This unexpected intercomponent C-H insertion illustrates the distinct reactivity brought to the Co /porphyrinate catalyst by the mechanical bond.

A new chloro-bridged heterobimetallic Cu(II)Re(IV) chain of formula {Cu(pyim)(Him)2ReCl6}n·MeCN (·MeCN) has been prepared and magnetostructurally characterised. Compound is the first example of the [Re(IV)Cl6](2-) anion acting as a metalloligand towards a paramagnetic metal ion.

The reaction of Mn(ClO4)2·6H2O, a derivatised phenolic oxime (R-saoH2) and the ligand tris(2-pyridylmethyl)amine (tpa) in a basic alcoholic solution leads to the formation of a family of cluster compounds of general formula [Mn(III)2O(R-sao)(tpa)2](ClO4)2 (1, R = H; 2, R = Me; 3, R = Et; 4, R = Ph). The structure is that of a simple, albeit asymmetric, dimer of two Mn(III) ions bridged through one μ-O(2-) ion and the -N-O- moiety of the phenolic oxime. Magnetometry reveals that the exchange interaction between the two Mn(III) ions in complexes 1, 3 and 4 is antiferromagnetic, but that for complex 2 is ferromagnetic. A theoretically developed magneto-structural correlation reveals that the dominant structural parameter influencing the sign and magnitude of the pairwise interaction is the dihedral Mn-O-N-Mn (torsion) angle. A linear correlation is found, with the magnitude of J varying significantly as the dihedral angle is altered. As the torsion angle increases the AF exchange decreases, matching the experimentally determined data. DFT calculations reveal that the dyz|π*|dyz interaction decreases as the dihedral angle increases leading to ferromagnetic coupling at larger angles.

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A 5,15‐bis(1,1′‐biphenyl)porphyrin‐based molecular clip covalently connected to a ditopic aliphatic ester loop moiety yields a semi‐rigid macrocycle with a well‐defined cavity. The resulting macrocycle fits the structural requirements for the preparation of porphyrinates capable of promoting formation of C−C bonds. To demonstrate the usefulness of porphyrin‐based macrocycles, an active‐metal‐template synthesis of rotaxanes through a redox non‐innocent carbene transfer reaction is described. Coordination of CoII ions into the porphyrin subunit followed by addition of appropriate monodentate nitrogen‐based additives to function as axial ligands enables the radical carbene transfer reactions to styrene derivatives to occur exclusively through the cavity of the macrocycle to afford cyclopropane‐linked rotaxanes in excellent 95 % yield. Investigation of the product distribution afforded from the rotaxane assembly reaction reveals how the redox cooperative action between the carbene species and the CoII ions can be manipulated to gain control over the radical‐type mechanism to favor the productive rotaxane forming process.

Two new dinuclear copper(II) metallacyclophanes with 1,4-disubstituted 9,10-anthraquinonebis(oxamate) bridging ligands are reported that can reversibly take and release electrons at the redox-active ligand and metal sites, respectively, to give the corresponding mono- and bis(semiquinonate and/or catecholate) Cu(II)2 species and mixed-valent Cu(II)/Cu(III) and high-valent Cu(III)2 ones. Density functional calculations allow us to give further insights on the dual ligand- and metal-based character of the redox processes in this novel family of antiferromagnetically coupled di- copper(II) anthraquinophanes. This unique ability for charge storage could be the basis for the development of new kinds of molecular spintronic devices, referred to as molecular magnetic capacitors (MMCs).

In this work, selective interactions between the constituents of the composite CNT@MnCu (2) prepared using carbon nonotubes (CNTs) (1) and the heterobimetallic chain [MnCu­(opba)] n (MnCu), opba = o-phenylenebis­(oxamate), were studied mainly by resonance Raman spectroscopy and high-resolution transmission electron microscopy (HRTEM). An apparent interaction between CNTs and MnCu complex with the wrapping of the former by the heterobimetallic complex was observed in the microscopy images. The resonance Raman data suggest that the interations between MnCu complex and the CNTs are selective, occurring mainly with metallic CNTs independently of the diameter and excitation energy. However, for semiconducting CNTs, these interactions solely occur with tubes having diameters higher than ca. 1.47 nm.