两对手性YbII对映体具有不同的近红外发光和圆偏振发光性能,二次谐波产生响应存在巨大差异

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Dalton Transactions Pub Date : 2023-11-09 DOI:10.1039/D3DT03324D
Xiaodi Du, Zhiqiang Zhang, Congli Gao, Fengcai Li and Xi-Li Li
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引用次数: 0

摘要

将对映体纯的单双齿N-供体配体(LR/LS)分别引入Yb(btfa)3(H2O)2和Yb(dbm)3(H_2O)中,分离出两对手性YbII对映体,即Yb(btfa)3LR/Yb(btfa)3LS(D-1/L-1)和[Yb(dbm)3LR]•[Yb氟丙酮,dbm-=二苯甲酰基甲烷酸酯,LR/LS=(−)/(+)-4,5-联吡啶-2-吡嗪。D-1/L-1是单核结构,YbIII离子是八配位的,而D-2/L-2显示含有Yb(dbm)3(LR/LS)和Yb(dbm)3(C2H5OH)部分的共晶结构,其中两个YbII离子分别为八配位和七配位。它们不仅具有不同的分子结构,而且具有不同的线性和非线性光学性能。手性单核D-1具有比手性共晶D-2更好的近红外光致发光(NIR-PL)和圆偏振发光(CPL)性能。更显著的是,D-1/L-1表现出大的二次谐波产生(SHG)响应(高达1.25/1.28×KDP),是D-2/L-2(0.07/0.08×KDP的18/16倍)。此外,D-2/L-2代表具有NIR-PL、NIR-CPL和SHG性质的镧系元素共晶配合物的第一个实例。
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Two pairs of chiral YbIII enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses†

By introducing enantiomerically pure mono-bidentate N-donor ligands (LR/LS) into Yb(btfa)3(H2O)2 and Yb(dbm)3(H2O), respectively, two pairs of chiral YbIII enantiomers, namely Yb(btfa)3LR/Yb(btfa)3LS (D-1/L-1) and [Yb(dbm)3LR]·[Yb(dbm)3(C2H5OH)]/[Yb(dbm)3LS]·[Yb(dbm)3(C2H5OH)] (D-2/L-2) were isolated, where btfa = 3-benzoyl-1,1,1-trifluoroacetonate, dbm = dibenzoylmethanate, and LR/LS = (−)/(+)-4,5-pinenepyridyl-2-pyrazine. D-1/L-1 possess mononuclear structures in which the YbIII ions are eight-coordinated, while D-2/L-2 show cocrystal structures containing Yb(dbm)3(LR/LS) and Yb(dbm)3(C2H5OH) moieties in which the two YbIII ions are eight and seven-coordinated, respectively. They not only feature different molecular structures but also present distinct linear and nonlinear optical performances. Chiral mononuclear D-1 has better near infrared photo-luminescence (NIR-PL) and circularly polarized luminescence (CPL) performances than chiral cocrystal D-2. More remarkably, D-1/L-1 show large second-harmonic generation (SHG) responses (up to 1.25/1.28 × KDP) 18/16 times those of D-2/L-2 (0.07/0.08 × KDP). In addition, D-2/L-2 represent the first examples of lanthanide cocrystal complexes with NIR-PL, NIR-CPL and SHG properties.

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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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