基于羧酸基-酚羟基配体Pr配合物的结构、荧光性质以及辅助配体的影响  

Structures,Fluorescence Properties and Influence of Auxiliary Ligand on Pr Complexes Based on Carboxylate-Phenol Ligand

作　　者：罗仕超 彭庆鹏 张洪涛 刘楚湖 江尚坤 王莹 关磊 LUO Shi-chao;PENG Qing-peng;ZHANG Hong-tao;LIU Chu-hu;JIANG Shang-kun;WANG Ying;GUAN Lei(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun 113001,China)

机构地区：[1]辽宁石油化工大学石油化工学院,辽宁抚顺113001

出　　处：《化学试剂》2024年第6期26-32,共7页Chemical Reagents

基　　金：辽宁省教育厅基本科研项目(LJKMZ20220738);辽宁石油化工大学创新创业训练计划项目(S202310148010)。

摘　　要：采用3,3′-偶氮双(6-羟基苯甲酸)二钠(Na_(2)H_(2)L)为配体,通过水热法与Pr^(3+)反应得到两个配合物[Pr(H_(2)L)0.5(L)0.5(H_(2)O)2]n(1)和Pr(H L)(phen)(H_(2)O)5·2H_(2)O(2)(phen=1,10-邻菲罗啉)。配合物1中,H_(2)L_(2)-阴离子作为四齿配体,2个羧酸基分别以μ2-η^(1)∶η^(1)的方式与Pr^(3+)配位,形成二维层状结构,并且L 4-阴离子作为桥连配体,利用羧酸基和酚羟基分别以μ2-η^(2)∶η^(1)和桥连模式将二维层中3个相邻的Pr^(3+)连接,将结构拓展成三维网络结构,其Schl fli符号为{4^(2)·8^(4)}{4^(6)·6^(6)·8^(3)}{4^(7)·6^(3)}2。引入phen分子,配合物2变为单核结构,phen与Pr^(3+)螯合配位,HL^(3-)作为单齿配体与Pr^(3+)配位。配合物1和2分别在6^(3)8和778 nm,652和781 nm处有Pr^(3+)的特征荧光发射峰,颜色落在色度图的橙色区域内,是^(1)S_(0)→^(1)I_(6)和^(1)D_(2)→3H 4能级跃迁所致。配合物2的荧光强度高于配合物1,且主峰红移14 nm,归因于phen的共轭体系以及与Pr^(3+)配位作用。Two complexes[Pr(H_(2)L)0.5(L)0.5(H_(2)O)2]n(1)and Pr(H L)(phen)(H_(2)O)5·2H_(2)O(2)(Na_(2)H_(2)L=3,3′-azobis(6-hydroxybenzoic acid)disodium,phen=1,10-phenanthroline)were synthesized by hydrothermal reaction with Pr^(3+)using Na_(2)H_(2)L as ligand.In complex 1,the H_(2)L_(2)-anions act as tetradentate ligands,which bind to Pr^(3+)ions through two carboxylate groups inμ2-η^(1)∶η^(1)coordination mode,forming a two-dimensional layered structure.Moreover,the L 4-anions serve as bridging ligands,which connect the three adjacent Pr^(3+)ions in two-dimensional layers via the carboxylate and phenol groups inμ2-η^(2)∶η^(1)and bridging fashions,respectively,expanding into a three-dimensional network structure with the Schl fli symbol of{4^(2)·8^(4)}{4^(6)·6^(6)·8^(3)}{4^(7)·6^(3)}2.The structure of complex 2 transforms into a mononuclear one by the introduction of phen molecules,where phen molecules chelate with Pr^(3+),while HL^(3-)anions act as monodentate ligands,coordinating with Pr^(3+).Complexes 1 and 2 exhibited the characteristic emissions of Pr^(3+)at 6^(3)8 and 778 nm,652 and 781 nm,which fall within the orange region of the CIE chromaticity diagram,corresponding to ^(1)S_(0)→^(1)I_(6) and^(1)D_(2)→3H 4 energy transitions,respectively.The fluorescence intensity of complex 2 was higher than complex 1,and the main peak had red-shift of 14 nm,which was attributed to the conjugated system of phen and its coordination with Pr^(3+).

关 键 词：镨离子 配位聚合物 三维结构 荧光 辅助配体 

分 类 号：O614.33[理学—无机化学]