Solid‐State Reversible Anion Exchange and Irreversible Anion Replacement in 1D Zinc(II) Coordination Polymers: Precursors for the Preparation of Zinc(II) Nanostructures

Interesting solid‐state reversible anion exchange and irreversible anion replacement in zinc coordination polymers from the ligand 2,5‐bis(3‐pyridyl)‐3,4‐diaza‐2,4‐hexadiene (bpdh) with different anions, [Zn(μ‐bpdh)(H 2 O) 4 ](NO 3 ) 2 · 2bpdh ( 1 ), [Zn(μ‐bpdh)(H 2 O) 4 ](ClO 4 ) 2 · 2bpdh ( 2 ), [Zn(μ‐bpdh) 2 (NCS) 2 ] n ( 3 ), [Zn(μ‐bpdh) 2 (N 3 ) 2 ] n ( 4 ), and [Zn(μ‐bpdh)(NO 2 ) 2 ] n ( 5 ), were studied. Compounds 3 – 5 were prepared by irreversible solid‐state anion replacement of either compound 1 or 2 with KSCN, NaN 3 , or NaNO 2 under mixing or grinding. Compounds 1 and 2 undergo reversible solid‐state anion exchange between ClO 4 – and NO 3 – . ZnO and ZnS nanoparticles were obtained by thermolyses of compounds 1 – 5 in oleic acid at 280 °C in air.