Trinucleating Copper: Synthesis and Magnetostructural Characterization of Complexes Supported by a Hexapyridyl 1,3,5‐Triarylbenzene Ligand

Abstract

Copper threesome: A hexapyridyl ligand based upon a 1,3,5‐triphenylbenzene framework coordinates three metal centers in a constrained environment (see picture). The tricopper(I) complex reduces dioxygen to form a tricopper(II) cluster. The capping anions affect the magnetism and EPR spectra of these species and reveal a linear dependence between the antiferromagnetic exchange parameter and the Cu‐O‐Cu angles.

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn3MOn Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

“…Improving upon the published procedures, [13,14] in the glovebox, a 1L Erlenmeyer flask was equipped with a stir bar and charged with 1,3,5-tris(2-bromophenyl)benzene (8.83 g, 16.26 mmol) and Et 2 O (325 mL). The off-white suspension was frozen in the cold well.…”

“…Spectral features match those found in previous work. [13,14] 4.2 Synthesis of LMn II 3 (OAc) 3 (1).…”

Trinuclear first row transition metal complexes of a hexapyridyl, trialkoxy 1,3,5-triarylbenzene ligand

“…1,3,5-tris(2-(di(2-pyridyl)hydroxymethyl)phenyl)benzene (H 3 L, Scheme 1) is accessible in two steps from commercially available starting materials. 3 Trinuclear copper complexes supported by framework L have been synthesized containing a conserved Cu 3 (m-OR) 3 central moiety; varying the capping anions from halides, phosphate, tetrafluoroborate, and triflate causes subtle structural changes that affect the magnetism of these complexes. 3 Protonated and deprotonated dipyridylhydroxymethyl moieties are known to exhibit an array of coordination modes, from tridentate N,O,N coordination of a single metal center to more complicated bridging patterns of up to three metals.…”

“…3 Trinuclear copper complexes supported by framework L have been synthesized containing a conserved Cu 3 (m-OR) 3 central moiety; varying the capping anions from halides, phosphate, tetrafluoroborate, and triflate causes subtle structural changes that affect the magnetism of these complexes. 3 Protonated and deprotonated dipyridylhydroxymethyl moieties are known to exhibit an array of coordination modes, from tridentate N,O,N coordination of a single metal center to more complicated bridging patterns of up to three metals. 4 Although the M II 3 (m-OR) 3 structural motif is commonly found in higher nuclearity clusters in complexes of 2,2 0 -dipyridylketone 4 and as part of self-assembled tetranuclear clusters such as cubanes 5 and defective dicubanes, 6 the motif is less common in trinuclear complexes.…”

“…3 Protonated and deprotonated dipyridylhydroxymethyl moieties are known to exhibit an array of coordination modes, from tridentate N,O,N coordination of a single metal center to more complicated bridging patterns of up to three metals. 4 Although the M II 3 (m-OR) 3 structural motif is commonly found in higher nuclearity clusters in complexes of 2,2 0 -dipyridylketone 4 and as part of self-assembled tetranuclear clusters such as cubanes 5 and defective dicubanes, 6 the motif is less common in trinuclear complexes. 7 To further investigate the metal coordination potential of H 3 L and its control over cluster nuclearity, trinuclear complexes of L containing other first row transition metals were targeted.…”