Wu Zhao-Feng, Huang Xiao-Ying
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, the Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China.
Dalton Trans. 2017 Sep 26;46(37):12597-12604. doi: 10.1039/c7dt02800h.
Herein, the solvothermal preparations, crystal structures, and fluorescence properties of three Mg-Zn heterometallic coordination polymers (CPs), i.e. [MgZn(OH)(1,4-NDC)(HO)]·6HO (1), [MgZn(1,4-NDC)(dppe)(CHOH)] (2), and [MgZn(1,4-NDC)(py)]·1.5py (3), based on the mixed ligands of 1,4-naphthalene dicarboxylic acid (1,4-HNDC) and N-containing ligands of 1,3-di(4-pyridyl)propane (dppe) or pyridine (py) are presented. In the title compounds, Zn and Mg are statistically distributed, as confirmed by single crystal analysis, and the ratios of Zn and Mg have been identified by inductively coupled plasma (ICP) measurements. In compound 1, the metal ions are tetra- or hexa-coordinated by the oxygen atoms of the carboxylate and μ-OH group to form a one-dimensional (1D) ribbon, and these 1D ribbons are further bridged by 1,4-NDC linkers to grow into a 3D framework with 1D channels along the b axis. In compounds 2 and 3, the metal ions also adopt tetra- or hexa-coordination modes and are inter-bridged by carboxylate oxygen atoms to form a tri-nuclear secondary building unit (SBU). Due to the introduction of N-containing ligands acting as terminal molecules, these SBUs are linked by 1,4-NDC ligands to form a 2D network. Photoluminescence (PL) studies indicated that the title compounds showed strong blue emissions. Significantly, compound 1 demonstrated sensitive fluorescence sensing for Fe, carbon disulfide (CS), and nitroaromatic compounds at low concentrations. The fluorescence sensing properties of compound 2 were also comparatively investigated in detail.
本文报道了基于1,4-萘二甲酸(1,4-HNDC)与含氮配体1,3-二(4-吡啶基)丙烷(dppe)或吡啶(py)的混合配体的三种镁锌异金属配位聚合物(CPs),即[MgZn(OH)(1,4-NDC)(H₂O)]·6H₂O(1)、[MgZn(1,4-NDC)(dppe)(CH₃OH)](2)和[MgZn(1,4-NDC)(py)]·1.5py(3)的溶剂热制备、晶体结构及荧光性质。在标题化合物中,通过单晶分析证实锌和镁呈统计分布,且锌和镁的比例已通过电感耦合等离子体(ICP)测量确定。在化合物1中,金属离子通过羧酸根和μ-OH基团的氧原子进行四配位或六配位,形成一维(1D)带状结构,这些1D带状结构进一步通过1,4-NDC连接体桥连,沿b轴生长成具有1D通道的三维框架。在化合物2和3中,金属离子也采用四配位或六配位模式,并通过羧酸根氧原子相互桥连形成三核二级构筑单元(SBU)。由于引入了作为端基分子的含氮配体,这些SBU通过1,4-NDC配体连接形成二维网络。光致发光(PL)研究表明,标题化合物表现出强烈的蓝色发射。值得注意的是,化合物1对低浓度的铁、二硫化碳(CS)和硝基芳香化合物表现出灵敏的荧光传感性能。还对化合物2的荧光传感性能进行了比较详细的研究。