Aromatic Chelator-Specific Lattice Architecture and Dimensionality in Binary and Ternary Cu(II)-Organophosphonate Materials

Synthetic
efforts linked to the design of defined lattice dimensionality and
architecture materials in the binary/ternary systems of Cu­(II) with
butylene diamine tetra­(methylene phosphonic acid) (H8BDTMP)
and heterocyclic organic chelators (pyridine and 1,10-phenanthroline)
led to the isolation of new copper organophosphonate compounds, namely,
Na6[Cu2(BDTMP)­(H2O)4]·[Cu2(BDTMP)­(H2O)4]0.5·26H2O (1), [Cu2(H4BDTMP)­(py)4]·2H2O (2), and [Cu2(H4BDTMP)­(phen)2]n·6.6nH2O·1.5nMeOH (3). 1–3 are the
first compounds isolated from the Cu­(II)-BDTMP family of species.
They were characterized by elemental analysis, spectroscopic techniques
(FT-IR, UV–vis), magnetic susceptibility, TGA-DTG, cyclic voltammetry,
and X-ray crystallography. The lattice in 1 reveals the
presence of discrete dinuclear Cu­(II) units bound to BDTMP8– and water molecules in a square pyramidal geometry. The molecular
lattice of 2 reveals the presence of ternary dinuclear
assemblies of Cu­(II) ions bound to H4BDTMP4– and pyridine in a square pyramidal environment. The molecular lattice
of 3 reveals the presence of dinuclear assemblies of
Cu­(II) ions bound to H4BDTMP4– and 1,10-phenanthroline
in a square pyramidal environment, with the organophosphonate ligand
serving as the connecting link to abutting dinuclear Cu­(II) assemblies
in a ternary polymeric system. The magnetic susceptibility data on 1, 2, and 3 suggest that compounds 1 and 3 exhibit a stronger antiferromagnetic
behavior than 2, which is also confirmed from magnetization
measurements. The physicochemical profiles of 1–3 (a) earmark the influence of the versatile H8BDTMP ligand as a metal ion binder on the chemical reactivity in
binary and ternary systems of Cu­(II) in aqueous and nonaqueous media
and (b) denote the correlation of ligand hydrophilicity, aromaticity,
denticity, charge, and H-bonding interactions with emerging defined
Cu­(II)–H8BDTMP structures of distinct lattice identity
and spectroscopic-magnetic properties. Collectively, such structural
and chemical factors formulate the interplay and contribution of binary
and ternary interactions to lattice architecture and specified properties
of new Cu­(II)–organophosphonate materials with defined 2D–3D
dimensionality.

针对铜(II)与丁二胺四(亚甲基膦酸)(butylene diamine tetra(methylene phosphonic acid), H8BDTMP)以及杂环有机螯合剂（吡啶、1,10-菲咯啉）构成的二元/三元体系，开展具有明确晶格维度与架构的材料合成设计工作，成功分离得到三种新型有机膦酸铜化合物，分别为Na6[Cu2(BDTMP)(H2O)4]·[Cu2(BDTMP)(H2O)4]0.5·26H2O（1）、[Cu2(H4BDTMP)(py)4]·2H2O（2）以及[Cu2(H4BDTMP)(phen)2]n·6.6nH2O·1.5nMeOH（3）。上述化合物1~3均为Cu(II)-BDTMP物种家族中首次被分离得到的成员。所有化合物均通过元素分析、光谱技术（傅里叶变换红外光谱（FT-IR）、紫外-可见光谱（UV–vis））、磁化率测试、热重-微分热重分析（TGA-DTG）、循环伏安法以及X射线晶体学完成了表征。化合物1的晶格中存在与BDTMP8–及水分子以四方锥几何构型结合的离散双核Cu(II)单元。化合物2的分子晶格则包含由双核Cu(II)离子与H4BDTMP4–及吡啶以四方锥配位环境结合形成的三元双核组装体。化合物3的分子晶格中，双核Cu(II)离子与H4BDTMP4–及1,10-菲咯啉以四方锥配位环境结合形成双核组装体，其中有机膦酸配体作为连接桥，将相邻的双核Cu(II)组装体联结为三元聚合体系。针对化合物1、2、3的磁化率测试数据表明，化合物1和3相较于2表现出更强的反铁磁性行为，该结论也通过磁化强度测试得到了验证。化合物1~3的理化特性（a）表明多功能配体H8BDTMP作为金属离子结合位点，对水相及非水相体系中Cu(II)的二元与三元体系化学反应活性具有显著调控作用；（b）揭示了配体的亲水性、芳香性、配位数、电荷以及氢键相互作用，与具有独特晶格特征及光谱-磁学性能的新型Cu(II)-H8BDTMP结构之间的内在关联。综上，此类结构与化学因素共同阐明了二元与三元相互作用对具有明确2D~3D维度的新型Cu(II)-有机膦酸材料的晶格架构与特定性能的调控作用与内在关联。