手性炔银链的构筑及手性光学性质调控  

Construction of chiral alkynyl silver chains and modulation of chiral optical properties

作　　者：王栋恒 李思 臧双全[1] WANG Dongheng;LI Si;ZANG Shuangquan(College of Chemistry,Zhengzhou University,Zhengzhou 450001,China)

机构地区：[1]郑州大学化学学院,郑州450001

出　　处：《无机化学学报》2025年第1期131-140,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.92356304,92061201,U21A20277,22101264);河南省中原千人计划(No.234000510007);中原英才计划-中原青年博士后创新人才项目资助。

摘　　要：基于手性配体诱导策略,利用3对不同末端基团的芳香炔配体[4‑乙炔基‑2R‑异吲哚啉‑1,3‑二酮,R=1‑羟基‑2‑丙基(L/D‑1)、1‑羟基‑3‑甲基‑2‑丁基(L/D‑2)、2‑羟基‑1‑苯乙基(L/D‑3)]和2,2'‑联吡啶(bpy)分别与高氯酸银(AgClO_(4))反应,成功得到3对绿色发光的手性炔银链{[Ag_(10)(bpy)_(10)(L/D‑1)_(4)](ClO_(4))_(6)·H_(2)O}_(n)(L/D⁃Ag_(10)⁃1)、{[Ag_(10)(bpy)_(10)(L/D‑2)_(4)](ClO_(4))_(6)·3CH_(3)OH}_(n)(L/D⁃Ag_(10)⁃2)和{[Ag_(10)(bpy)_(10)(L/D‑3)_(4)](ClO_(4))_(6)}_(n)(L/D⁃Ag_(10)⁃3)。有趣的是,随着炔基配体末端基团空间位阻的增大,聚合物骨架的扭曲程度以及链间相互作用明显提高,并伴随着吸收不对称因子(g_(abs))和发光不对称因子(g_(lum))的逐渐增加。另外,通过溶解再组装策略,L/D⁃Ag_(10)⁃2在DMF‑H_(2)O体系中表现出明显的聚集诱导发光现象,并且新的聚集体显示出明显的手性光学性能提升,组装体的|g_(abs)|和|g_(lum)|分别是晶体状态的74.6倍和12.5倍。Based on the chiral ligand‑induced strategy,three pairs of green‑emitting chiral alkynyl silver chains{[Ag_(10)(bpy)_(10)(L/D‑1)_(4)](ClO_(4))_(6)·H_(2)O}_(n)(L/D⁃Ag_(10)⁃1),{[Ag_(10)(bpy)_(10)(L/D‑2)_(4)](ClO_(4))_(6)·3CH_(3)OH}_(n)(L/D⁃Ag_(10)⁃2),and{[Ag_(10)(bpy)_(10)(L/D‑3)_(4)](ClO_(4))_(6)}_(n)(L/D⁃Ag_(10)⁃3)were successfully obtained by reacting three pairs of aromatic alkyne ligands with different terminal groups[4‑ethynyl‑2R‑isoindoline‑1,3‑dione,R=1‑hydroxy‑2‑propyl(L/D‑1),1‑hydroxy‑3‑methyl‑2‑butyl(L/D‑2),2‑hydroxy‑1‑phenylethyl(L/D‑3)],and 2,2'‑bipyridine(bpy)with silver perchlorate(AgClO_(4)).The crystal structure was determined by single‑crystal X‑ray diffraction(SCXRD),and the molecular formula composition was demonstrated by thermogravimetric analysis(TGA),elemental analysis(EA),and 1H NMR.By circular dichroism(CD)and circularly polarized luminescence(CPL)spectroscopy,it was demonstrated that the design approach using a chiral alkyne‑based ligand in combination with an Agwas effective in inducing chirality in the polymer.Interestingly,the degree of distortion of the polymer backbone as well as the interchain interactions were significantly increased with the increase of the spatial site resistance of the terminal group of the alkyne‑based ligand,which was accompanied by a gradual increase in the values of the absorption asymmetry factor(g_(abs))and the luminescence asymmetry factor(g_(lum)).In addition,L/D⁃Ag_(10)⁃2 exhibited obvious aggregation‑induced luminescence in the DMF‑H_(2)O system through the dissolution‑reassembly strategy,and the new aggregates showed obvious enhancement of the chiral optical properties,with the|g_(abs)|and|g_(lum)|values of the aggregates being 74.6 times and 12.5 times higher than those of the crystalline state.CCDC:2392365,L⁃Ag_(10)⁃1;2392366,D⁃Ag_(10)⁃1;2392316,L⁃Ag_(10)⁃2;2392317,D⁃Ag_(10)⁃2;2392165,L⁃Ag_(10)⁃3;2392164,D⁃Ag_(10)⁃3.

关 键 词：一维结构 炔银 手性 光致发光 

分 类 号：O614.122[理学—无机化学]