New Types of Metal Squarato-phosphonates: Condensation of Aminodiphosphonate with Squaric Acid under Hydrothermal Conditions

The syntheses and crystal structures of the first copper(I) phosphonate, Cu2(H3L)(bipy)2·2H2O 1 (H5L = C4HO3N(CH2PO3H2)2), which is also the first example of metal phosphonates formed by a type of organic reaction, and a novel
luminescent Mn(II) squarate diphosphonate, {Mn[NH(CH2PO3H)2](H2O)2}2{Mn(C4O4)(H2O)4}·(C4H2O4) 2, have been
reported. The structure of 1 features a layer architecture in which the Cu(I) centers are three coordinated, and the
newly formed ligand acts as a bidentate metal linker. Compound 2 is composed of 1D chains of Mn[NH(CH2PO3H)2](H2O)2, 1D chains of {Mn(C4O4)(H2O)4}, as well as the neutral squaric acid molecules. These three types
of building units are interconnected via hydrogen bonding.

本文报道了首例亚膦酸铜(I)配合物Cu₂(H₃L)(联吡啶(bipy))₂·2H₂O（1）（其中H₅L = C₄HO₃N(CH₂PO₃H₂)₂）——该配合物亦是首例通过一类有机反应构建的金属膦酸盐体系——以及一种新型发光型方酸二膦酸锰(II)配合物{Mn[NH(CH₂PO₃H)₂](H₂O)₂}₂{Mn(C₄O₄)(H₂O)₄}·(C₄H₂O₄)（2）的合成与晶体结构。配合物1的晶体结构呈现层状骨架，其中Cu(I)中心为三配位模式，新生成的配体充当双齿金属连接体。配合物2由三类结构基元构成：Mn[NH(CH₂PO₃H)₂](H₂O)₂一维链、{Mn(C₄O₄)(H₂O)₄}一维链，以及中性方酸分子。这三类结构基元经由氢键作用相互连接。