A series of iron­(III) chloride and iron­(III) μ-oxo compounds supported by tetradentate amino-bis­(phenolate) ligands containing a homopiperazinyl backbone were prepared and characterized by electronic absorption spectroscopy, magnetic moment measurement, and MALDI-TOF mass spectrometry. The solid-state structures of three iron­(III) μ-oxo compounds were determined by single crystal X-ray diffraction and revealed oxo-bridged bimetallic species with Fe–O–Fe angles between 171.7 and 180°, with the iron centers in distorted square pyramidal environments. Variable temperature magnetic measurements show the oxo complexes exhibit strong antiferromagnetic coupling between two high-spin S = 5/2 iron­(III) centers. The oxo complexes exhibit poor activity for the reaction of carbon dioxide and epoxides in the presence of a cocatalyst, under solvent free conditions to yield cyclic carbonates. The least active iron oxo compound bears tert-butyl groups on the phenolate donors, and we propose that steric congestion around the iron center reduces catalytic activity in this case. We provide evidence that an epoxide deoxygenation step occurs when employing monometallic iron­(III) chlorido species as catalysts. This affords the corresponding μ-oxo compounds which can then enter their own catalytic cycle. Deoxygenation of epoxides during their catalytic reactions with carbon dioxide is frequently overlooked and should be considered as an additional mechanistic pathway when investigating catalysts.

A bromonium oxidizing agent was used to produce a ring-oxidized zinc phthalocyanine (PcZn), [PcZn(solvent)][BAr] (1·solvent), in good yield. This material is dimeric in the solid state with one axially coordinated solvent [tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME)] and close intradimer ring-ring distances of 3.18 and 3.136 Å (THF and DME respectively); this proximity facilitates strong antiferromagnetic coupling to yield diamagnetic dimers. 1·THF is present in solution as a monomer and a dimer. In CHCl, the dimer is favored above 0.1 mM, and it is almost exclusively present in solvents with a high dielectric constant such as acetonitrile. The material 1·THF/DME decomposes in DME to a meso-nitrogen-protonated species, [HPcZn(DME)][BAr] (2), which was isolated and represents the first example of such a structurally characterized, protonated, unsubstituted PcM complex. A partially oxidized dimer or "pimer" [(PcZn(DME))][BAr] (3) was also structurally characterized and has a intradimer ring-ring distance of 3.192 Å, similar to 1·THF/DME. Dimer 3 also represents the first isolated PcM-based pimer. Electron paramagnetic resonance analysis of a 1.0 mM solution of 1·DME in DME showed the production of 3 over hours by the combination of 1·DME and 2 in solution.

The design and synthesis of a supramolecular square was achieved by coordination-driven assembly of redox-active nickel(ii) salen linkers and (ethylenediamine)palladium(ii) nodes.

The preparation and structural characterization of as eries of lanthanide and uranium(IV)p hthalocyanine halide complexes were achieved by reaction of the corresponding metal halide with Li 2 Pc. Ap reliminarys urvey of their reactivity includes ring reduction of Li(THF) 4 [PcUCl 3 ] with KC 8 leading to the first structurally characterized Pc 4À actinide complex, hydrolysis of PcDyCl(DMSO) to PcDyOH(H 2 O) 3 and preparation of au nique trimeric triangular Li(PcDy) 3 (OH) 4 (H 2 O) cluster.Macrocyclic phthalocyanines, porphyrins, andt heir metal complexes are widelyu sed for applications, such as dyes, pigments, [1] catalysts, [2] and photosensitizes for photodynamic cancert herapy with singlet oxygen. [3] The vast majority of metallophthalocyanine (PcM) complexes utilize transition metals,w ith ap articularf ocus on the late first row elements due to their good fit with the Pc-holeand their very high stability. Pc-complexes of fe lements (Ln = lanthanide;A c = actinide), which were first reported in 1965, [4] are much less investigated, with the notable exceptiono fb is-phthalocyanine sandwich complexes of the form [Pc 2 Ln] À and their more elaborate multidecker analogues, such as Pc 3 Ln 2 , [4,5] whicha re favoured due to the large ionic radii andh igh coordination numbers of the f-block elements, anda re of particulari nterest for single-molecule-magnet applications (especially for Ln = Dy,T b, Er). [6,7] However, furtherc hemistry at the metal site is limited in these Pc 2 -based systemsd ue to the steric and electronic saturation of the Ln centre. The less developed mono-PcLnXo rP cAcX 2 systems have mostly focused on oxy-anions as the axial X-group, with afew examples of X = halide; [8,9] however,t here are very few structurally characterizeds ystems, and their reactivity chemistry is ripe for furtherd evelopment. Herein, we report the synthesis, structure, and preliminaryr eactivity survey of PcM halide materials for both 4f and 5f metals, illustrating a Scheme1.Synthesis of PcDyCl(DMSO), PcErCl(THF), and Li(THF) 4 [PcUCl 3 ]. "Solvent" in PcLn-product = DMSO or THF,depending on the recrystallization conditions(seetext).[a] Dr.