Department of Chemistry, University of Jammu, Baba Sahib Ambedkar Road, Jammu-180006, India.
Dalton Trans. 2018 Sep 11;47(35):12318-12336. doi: 10.1039/c8dt02429d.
Single crystal X-ray diffraction studies reveal the formation of six new coordination polymers (CPs) with the general formulas [Dy(3,5-pdc)(3,5-pdcH)(H2O)2]n·nH2O (1), [Pr2(3,5-pdc)3(H2O)2]n·2n(H2O) (2), [Sm2(3,5-pdc)3(H2O)3]n·nH2O (3), {[Eu2(3,5-pdc)3(H2O)3(CH3CHO)]n·n[2(H2O)(DMF)]} (4), {[Gd2(3,5-pdc)3 (H2O)2]n·2nH2O} (5) and [Er(3,5-pdc)(adip)0.5(H2O)]n (6) (where 3,5-pdc2- = fully deprotonated; 3,5-pdcH- = partially deprotonated 3,5-pyridinedicarboxylic acid; adip2- = fully deprotonated adipic acid; and DMF = dimethylformamide) by solvothermal self-assembly of lanthanide ions with rigid 3,5-pyridinedicarboxylic acid as a linker and adipic acid as an auxiliary flexible spacer (only coordinated in CP 6). CPs 1 and 2 crystallize in the triclinic P1[combining macron] space group, whereas CPs 3, 4 and 6 crystallize in the monoclinic P21/n, P21/c and C2/c space groups, respectively. CP 5 exhibits the trigonal R3 space group. The 3,5-pdc ligand exhibits eight diverse coordination modes in CPs 1-6, whereas the adipic acid spacer in CP 6 shows only one coordination mode (μ4-κO:κO,O:κO:κO,O). The organic ligands interconnect with metal ions to generate 3D metal-organic frameworks with a variety of intriguing topologies. Theoretical studies, DFT calculations and Hirshfeld surface analysis support the structures adopted by the various CPs. CPs 3 (Sm) and 4 (Eu) emit strong ligand-sensitized characteristic f-f luminescence. Weak ferromagnetic interactions have been studied at low temperatures for CP 1 and CP 5.
单晶 X 射线衍射研究揭示了六种新配位聚合物 (CPs) 的形成，其通式为 [Dy(3,5-pdc)(3,5-pdcH)(H2O)2]n·nH2O（1）、[Pr2(3,5-pdc)3(H2O)2]n·2n(H2O)（2）、[Sm2(3,5-pdc)3(H2O)3]n·nH2O（3）、{[Eu2(3,5-pdc)3(H2O)3(CH3CHO)]n·n[2(H2O)(DMF)]}（4）、{[Gd2(3,5-pdc)3(H2O)2]n·2nH2O}（5）和 [Er(3,5-pdc)(adip)0.5(H2O)]n（6）（其中 3,5-pdc2- = 完全去质子化；3,5-pdcH- = 部分去质子化 3,5-吡啶二甲酸；adip2- = 完全去质子化 己二酸；DMF = 二甲基甲酰胺），通过镧系元素离子与刚性 3,5-吡啶二甲酸作为连接体和己二酸作为辅助柔性间隔物（仅在 CP 6 中配位）的溶剂热自组装。CPs 1 和 2 结晶于三斜晶系 P1[combining macron]空间群，而 CPs 3、4 和 6 分别结晶于单斜晶系 P21/n、P21/c 和 C2/c 空间群。CP 5 呈现三角 R3 空间群。3,5-吡啶二甲酸配体在 CPs 1-6 中表现出八种不同的配位模式，而己二酸间隔物在 CP 6 中仅表现出一种配位模式（μ4-κO:κO,O:κO:κO,O）。有机配体与金属离子相互连接，生成具有多种有趣拓扑结构的 3D 金属有机骨架。理论研究、DFT 计算和 Hirshfeld 表面分析支持各种 CPs 所采用的结构。CPs 3（Sm）和 4（Eu）发射强烈的配体敏化特征 f-f 荧光。对 CP 1 和 CP 5 进行了低温下的弱铁磁相互作用研究。
