Luminescent Open‐Framework Antiferromagnet – Hydrothermal Syntheses, Structures, and Luminescent and Magnetic Properties of Two Novel Coordination Polymers: [Zn(pdoa)(bipy)] n and {[Mn(pdoa)(bipy)](bipy)} n [pdoa = 2,2′‐(1,3‐phenylenedioxy)bis(acetate); bipy = 4,4′‐bipyridine]

Two coordination polymers of mixed ligands, 2,2′‐(1,3‐phenylenedioxy)bis(acetate) (pdoa) and 4,4′‐bipyridine (bipy),namely [Zn(pdoa)(bipy)] n ( 1 ) and {[Mn(pdoa)(bipy)](bipy)} n ( 2 ), have been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and IR spectra. Complex 1 crystallizes in the triclinic space group P $\bar {1}$ with a = 6.8826(18) Å, b = 11.202(3) Å, c = 12.295(3) Å, α = 86.854(4)°, β = 85.759(5)°, γ = 72.629(4)° and is a novel folded‐paper‐shaped coordination compound with polymeric sheets formed by the five‐coordinate Zn II centers and bridging pdoa and bipy. Complex 2 crystallizes in the monoclinic space group P 2 1 / c with a = 11.507(2) Å, b = 23.254(5) Å, c = 9.8710(19) Å, β = 96.418(4)° and exhibits a robust three‐dimensional framework with nanosized rectangular channels (11.627 × 11.507 Å). They both display blue fluorescent emission and could be considered as new luminescent materials. In addition, the magnetic properties of complex 2 were investigated and the magnetic susceptibility data were rationally fitted with g = 2.072(5), J = –1.11(4) cm –1 , and zJ′ =–0.161(7) cm –1 , showing it is an unprecedented luminescent open‐framework antiferromagnet.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)