2-萘甲酸/1,10-菲啰啉共同构筑Mn(II)配合物的合成及固态发光

摘要/Abstract

摘要： 在溶剂热条件下,以2-萘甲酸(HL)与1,10-菲啰啉(phen)为配体、碳酸锰为金属源合成了一例双核锰配合物[Mn₂(L)₄(phen)₂(H₂O)₂](1)。通过单晶X射线衍射、元素分析、傅里叶变换红外光谱、粉末X射线衍射和热重分析等对配合物1进行结构表征。单晶衍射分析表明配合物1属于三斜晶系,P1空间群,晶胞参数为a=0.769 89(5) nm,b=1.175 86(5) nm,c=1.668 30(9) nm,α=107.074(5)°,β=96.167(5)°,γ=106.901(5)°。不对称单元由一个锰离子、两个2-萘甲酸根、一个1,10-菲啰啉和一个水分子组成,Mn(II)呈扭曲的八面体构型。两个不对称单元之间通过羧基氧原子桥接形成双核分子,双核结构之间通过π…π堆积作用形成2D超分子结构。荧光光谱分析结果表明:配合物1具有良好的荧光性能,最大发射波长为416 nm(λ_ex=302 nm)。热重分析表明配合物1能够稳定到117 ℃,之后开始失水(失水量为3.18%),脱水之后的结构能稳定到223 ℃,之后有机骨架开始坍塌。Hirshfeld表面分析研究了分子间的相互作用。

关键词: 双核Mn(II)配合物, 溶剂热合成, 晶体结构, 2-萘甲酸, 荧光性质, 表面分析

Abstract: A case of binuclear manganese complex [Mn₂(L)₄(phen)₂(H₂O)₂] (1) was synthesized under solvothermal conditions with 2-naphthalic acid (HL) and 1,10-phenanthrenoline (phen) as ligands and manganese carbonate as the metal source. Complex 1 was characterized by single-crystal X-ray diffraction, elemental analysis, fourier transform infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analysis. single-crystal X-ray diffraction shows that complex 1 belonged to the triclinic crystal system P1 space group and the crystal cell parameters are a=0.769 89(5) nm, b=1.175 86(5) nm, c=1.668 30(9) nm, and α=107.074(5)°,β=96.167(5)°,γ=106.901(5)°. The asymmetric unit consists of a manganese ion, two 2-naphthoate anions, one 1,10-phenanthroline ligand and one water molecule, and Mn(II) atom is in a distorted octahedral configuration. The asymmetric units are bridged by carboxyl-oxygen atoms to form a dinuclear structure and then the binuclear structures are linked into a 2D supramolecular structure through π…π stacking interactions. The results of fluorescence spectroscopy show that complex 1 has good fluorescence performance and the maximum emission wavelength is 416 nm (λ_ex=302 nm). Thermogravimetric analysis shows that complex 1 remains stable to 117 ℃, and then begins to lose water of 3.18%, the structure after dehydration can stabilize at 223 ℃, after which the organic framework begins to collapse. Hirshfeld surface analysis is used to study the interaction between molecules.

Key words: binuclear Mn(II) complex, solvothermal synthesis, crystal structure, 2-naphthalic acid, fluorescent property, surface analysis

中图分类号:

O641.4

任娜娜, 江旭滢, 宋合兴, 史福林, 王雅茹, 孙赞. 2-萘甲酸/1,10-菲啰啉共同构筑Mn(II)配合物的合成及固态发光[J]. 人工晶体学报, 2024, 53(10): 1776-1783.

REN Nana, JIANG Xuying, SONG Hexing, SHI Fulin, WANG Yaru, SUN Zan. Synthesis and Solid-State Luminescence of Mn(II) Complex Constructed by 2-Naphthalic Acid/1,10-Phenanthroline[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(10): 1776-1783.

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