Study on the Crystal Structure of a Macrocycle and Tyrosinase Activity of Its Dinuclear Copper Complexes

A ring‐contracted form macrocycle, 29,30‐dioxo‐3,6,9,17,20,23,29,30‐octaazapentacyclo[23,3,1,1 11,15 ,0 2,6 ,0 16,20 ]‐triacontaneocta‐1(28),9,11(12),13,15(30),23,25(29),26‐ene (L) was synthesized by condensation of diethyltriamine with pyridine‐1‐oxide‐2,6‐dicarboxaldehyde. A porous three‐dimensional layer structure in its crystal was formed by self‐assembly through hydrogen bonds and π‐π interaction. Its dinuclear copper(I) complex [Cu 2 L(MeOH) 2 ](BF 4 ) 2 ·2H 2 O and dinuclear‐copper(II) complex [Cu 2 L(MeOH) 2 ](ClO 4 ) 4 ·2H 2 O were obtained and could oxidize catalytically four phenolic substrates hydroquinone, 2‐methyl‐hydroquinone, 2,6‐di‐ tert ‐butylphenol and 2,6‐dimethylphenol, in a mixture of methanol and acetonitrile (V:V, 4:1). The copper(I) complex reacted with dioxygen to form an oxygenated species as an initial active intermediate for oxidation of the phenols. Oxidation of the substrates by the copper(II) complex produced a copper(I) complex and the oxidation products of the substrates.