Synthesis, Structures, and Magnetic Properties of End-to-End Azide-Bridged Manganese(III) Chains: Elucidation of Direct Magnetostructural Correlation

Abstract

The two one-dimensional chain compounds [Mn(L1)(N3)]·H2O (1·H2O; H2L1 = 2,2'-((1E,1'E)-ethane-1,2-diylbis(azan-1-yl-1-ylidene))bis(phenylmethan-1-yl-1-ylidene)diphenol) and [Mn(L2)(N3)] (2; H2L2 = 2,2'-((1E,1'E)-2,2-dimethylpropane-1,3-diyl)bis(azan-1-yl-1-ylidene)-bis(phenylmethan-1-yl-1-ylidene)diphenol) bridged by single end-to-end azides were prepared via a self-assembly process. Each Mn(III) ion exhibits a characteristic Jahn-Teller elongation along the chain direction. For both compounds, antiferromagnetic interactions between Mn(III) spins within a chain are transmitted through the azide ligands, together with the apparent occurrence of spin canting at low temperatures. Remarkably, the coupling constants (J) for 1 and 2 exceed those reported for end-to-end azide-linked Mn(III) systems. A systematic magnetostructural relationship based on the torsion angle is established in terms of the torsion angle Mn-N(ax)···N(ax)-Mn (ax = axial) for the first time.

Synthesis, Crystal Structure and Magnetic Properties of [Mn((1R, 2R)‐Salcy)N3/NCS] Complexes: Solvent Dependent Crystallization of Monomers, Chains and Dimers.

“…These chains with alternating short and long bonds stand alone with no significant interchain contacts (Figure S9). While dimeric repeat units have been previously reported for azide–, as well as cyanide chain polymers, they all have symmetric bridges.…”

“…A compilation of the geometric parameters for Mn(III)‐azido bridged chains have recently been published . The Mn−N−N bridging angles in 1 and 2 (Table ) are within the range or deviating only slightly from it.…”

Syntheses, Crystal Structures and Photophysical Aspects of Discrete and Polymeric Azido‐Bridged Zinc(II) and Cadmium(II) Complexes: Sensing Properties and Structural Resemblance

“…Self‐assembled supramolecular architectures are of great interest due to the aesthetic beauty and potential as functional materials. In supramolecules, the individual building blocks may be self‐assembled by covalent bonds, coordinate bonds and weak interactions like hydrogen bonds, π⋅⋅⋅π stacking interactions, halogen bonds, carbonyl⋅⋅⋅carbonyl interaction, etc . Coordination polymers, including metal organic frameworks, belong to a class of supramolecules in which the nodes are metal complexes and the linkers are bridging organic or inorganic ligands .…”

“…In supramolecules, the individual building blocks may be self‐assembled by covalent bonds, coordinate bonds and weak interactions like hydrogen bonds, π⋅⋅⋅π stacking interactions, halogen bonds, carbonyl⋅⋅⋅carbonyl interaction, etc . Coordination polymers, including metal organic frameworks, belong to a class of supramolecules in which the nodes are metal complexes and the linkers are bridging organic or inorganic ligands . Regarding inorganic bridging ligands, azide is a nice linker because it can coordinate to metal ions in various modes such as μ 1,1 ‐ (end‐on; commonly expressed as EO), μ 1,3 ‐ (end‐to‐end; commonly expressed as EE), μ 1,1,1 ‐, μ 1,1,3 ‐, μ 1,1,1,1 ‐, and μ 1,1,3,3 ‐ ,.…”

“…Coordination polymers, including metal organic frameworks, belong to a class of supramolecules in which the nodes are metal complexes and the linkers are bridging organic or inorganic ligands . Regarding inorganic bridging ligands, azide is a nice linker because it can coordinate to metal ions in various modes such as μ 1,1 ‐ (end‐on; commonly expressed as EO), μ 1,3 ‐ (end‐to‐end; commonly expressed as EE), μ 1,1,1 ‐, μ 1,1,3 ‐, μ 1,1,1,1 ‐, and μ 1,1,3,3 ‐ ,. Although several azido bridged coordination polymers as well as discrete systems have been reported previously, exploration of metallo‐azides always deserves attention because of the uncertainty of the product and accompanied probability of getting new types of structures and associated properties.…”