CAJ | 학술논문

报道了通过硫醇配体实现Cu纳米团簇发光特性的调控．光致发光谱（PL ）显示，在初始合成的2‐巯基‐5‐正丙烷基嘧啶（MPP）包覆的Cu纳米团簇溶液中逐渐增加十二硫醇（C12 SH）的浓度， Cu纳米团簇主发光峰的波长从623 nm逐渐蓝移到584 nm ．质谱结果显示，在配体交换过程前后， Cu纳米团簇中Cu原子数目保持不变，但随加入的C12 SH 的浓度增加，C12 SH 逐渐取代原有的MPP配体．通过X射线吸收精细结构（XAFS）技术进一步研究了溶液中发生配体交换过程的Cu纳米团簇的原子结构变化．结果表明，随着C12SH 浓度的增加，金属特征的Cu—Cu配位消失， Cu—S键长从0．228 nm缩短到0．224 nm ，同时Cu—S之间的电荷转移增多，C12 SH的刻蚀使得Cu纳米团簇的原子构型由初始的四面体排布展开为“—S—Cu—S—”一维链状结构，导致团簇整体发生金属性到共价性的转变，从而引起光致发光和吸收波长的显著蓝移．
보도료통과류순배체실현Cu납미단족발광특성적조공．광치발광보（PL ）현시，재초시합성적2‐구기‐5‐정병완기밀정（MPP）포복적Cu납미단족용액중축점증가십이류순（C12 SH）적농도， Cu납미단족주발광봉적파장종623 nm축점람이도584 nm ．질보결과현시，재배체교환과정전후， Cu납미단족중Cu원자수목보지불변，단수가입적C12 SH 적농도증가，C12 SH 축점취대원유적MPP배체．통과X사선흡수정세결구（XAFS）기술진일보연구료용액중발생배체교환과정적Cu납미단족적원자결구변화．결과표명，수착C12SH 농도적증가，금속특정적Cu—Cu배위소실， Cu—S건장종0．228 nm축단도0．224 nm ，동시Cu—S지간적전하전이증다，C12 SH적각식사득Cu납미단족적원자구형유초시적사면체배포전개위“—S—Cu—S—”일유련상결구，도치단족정체발생금속성도공개성적전변，종이인기광치발광화흡수파장적현저람이．
A study on tuning the fluorescence property of Cu nanoclusters by thiol ligands was presented . The photoluminescence (PL ) measurements show that the luminescent wave‐length of Cu nanoclusters capped by 2‐mercapto‐5‐n‐propylpyrimidine (M PP) is gradually blue‐shifted from 623 nm to 584 nm ,with increasing concentrations of dodecanethiol (C12 SH) added into the solution .The added thiol ligands ,as suggested by mass spectra ,do not change the number of Cu atoms in the clusters ,but replace some of the original MPP ligands .X‐ray absorption fine structure (XAFS) spectra reveal that with the increment of C12 SH ligands ,the Cu—Cu bonds disappear ,the Cu—S bond length is contracted from the original 0.228 nm to 0 .224 nm ,and the charge transfer from Cu to S is enhanced .Moreover ,the etching effect of C12 SH ligands leads to the change of atomic configuration of the Cu cores from the tetrahedron‐alike structure to the chain‐like structure of —S—Cu—S— .As a result ,the electronic features of the Cu clusters show a metallic‐to‐covalent transition , resulting in the blue‐shift of the luminescence and optical absorption wavelengths .