一例糠酸根稳定的六核铈氧簇的合成、结构及其显著的羟基自由基清除能力  

A hexanuclear cerium oxo cluster stabilized by furoate:Synthesis,structure,and remarkable ability to scavenge hydroxyl radicals

作　　者：高原[1] 刘一鸣 王春晖 韩哲 范超越 邱杰 GAO Yuan;LIU Yiming;WANG Chunhui;HAN Zhe;FAN Chaoyue;QIU Jie(School of Nuclear Science and Technology,Xi'an Jiaotong University,Xi'an 710049,China)

机构地区：[1]西安交通大学核科学与技术学院,西安710049

出　　处：《无机化学学报》2025年第3期491-498,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22076152,22276147,21806127)资助。

摘　　要：为了探究配体对铈氧簇的形成、结构和性质的影响及铈氧簇的潜在应用,使用糠酸(HFA)作为配体,通过溶液法合成了首例由糠酸根稳定的六核铈氧簇,并利用单晶X射线衍射、粉末X射线衍射、X射线光电子能谱、元素分析、热重和光谱等技术表征了其晶体NH_(4)[Ce_(6)O_(4)(OH)_(4)(FA)_(12)(NO_(3))(H_(2)O)]·5CH_(3)CN·12H_(2)O(1)的结构、组分和光谱性质。结果发现Ce离子即使在酸性条件下也具有较强的水解能力,其自身的水解缩合反应及与HFA的配位反应共同促使了化合物1的形成。通过芬顿反应产生羟基自由基(·OH)并采用甲基紫作为指示剂,进一步研究了化合物1清除自由基的能力。结果表明,其能有效地清除·OH,且清除效率随化合物1溶液体积的增加而提升。To explore the effects of ligands on the structure,properties,and applications of cerium oxo clusters,we synthesized the first cerium oxo cluster using furoate(FA)as ligands.The crystal NH_(4)[Ce_(6)O_(4)(OH)_(4)(FA)_(12)(NO_(3))(H_(2)O)]·_(5)CH_(3)CN·12H_(2)O(1)of this cluster were thoroughly characterized using techniques such as single-crystal X-ray diffraction,powder X-ray diffraction,X-ray photoelectron spectroscopy,elemental analysis,thermogravimetry,and spectroscopy.Single-crystal X-ray diffraction analysis revealed that compound 1 exhibits a hexanuclear cluster structure with a[Ce_(6)O_(4)(OH)_(4)]^(12+)core.As confirmed by the Raman spectrum,the Ce—O—Ce bond in this core suggests its formation via the hydrolysis reaction of Ce(Ⅳ)ions.This core is further stabilized by one water,one nitrate,and twelve FA groups to form the entire cluster structure.These results reveal that the hydrolysis and condensation reactions of Ce(Ⅳ)ions and their complex reaction with FA result in the formation of the cluster.The Fenton reaction was used to generate hydroxyl radicals,and methyl violet was utilized as an indicator to explore the free radical scavenging ability of compound 1.The UV-visible spectra indicated that the solution of compound 1 effectively scavenges hydroxyl radicals.As the volume of the compound 1 solution gradually increased from 50 to 2000μL,the scavenging efficiency rose from 8.32%to 91.06%.CCDC:2370679.

关 键 词：多金属氧簇 铈氧簇 水解反应 自由基清除 

分 类 号：O641.4[理学—物理化学]