Co-ligand tuned pyrimidine-2-carboxylate Mn(ii) complexes from a 2D 63 layer to an interpenetrated srs-net

Abstract

A 6³ 2D layer complex [Mn₃Cl₃(L₃)]_n·H₂O (1) (L = pyrimidine-2-carboxylate) was obtained by assembling 2-cyanopyrimidine and manganese chloride, in which the L ligands were generated in situ. In 1 six-membered Mn rings were constructed from Mn^II ions and L ligands, which were connected to each other by double chloride anions affording a 2D layer. When the chloride anions in 1 were substituted partly by formate, [Mn₄Cl₃L₄(HCO₂)]_n (2) was obtained. In 2, the L ligands bridge Mn^II to give a 1D chain, which was further connected by the double chloride anions and Cl/formate bridges to form a two-fold interpenetrated srs-net. Interestingly, 2 exhibits an obvious SHG response of approximately 0.8 times that of KDP. Furthermore, 2 is an antiferromagnet with a field induced spin flop transition.