Two pairs of chiral YbIII enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses†

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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Abstract

By introducing enantiomerically pure mono-bidentate N-donor ligands (L_R/L_S) into Yb(btfa)₃(H₂O)₂ and Yb(dbm)₃(H₂O), respectively, two pairs of chiral Yb^III enantiomers, namely Yb(btfa)₃L_R/Yb(btfa)₃L_S (D-1/L-1) and [Yb(dbm)₃L_R]·[Yb(dbm)₃(C₂H₅OH)]/[Yb(dbm)₃L_S]·[Yb(dbm)₃(C₂H₅OH)] (D-2/L-2) were isolated, where btfa⁻ = 3-benzoyl-1,1,1-trifluoroacetonate, dbm⁻ = dibenzoylmethanate, and L_R/L_S = (−)/(+)-4,5-pinenepyridyl-2-pyrazine. D-1/L-1 possess mononuclear structures in which the Yb^III ions are eight-coordinated, while D-2/L-2 show cocrystal structures containing Yb(dbm)₃(L_R/L_S) and Yb(dbm)₃(C₂H₅OH) moieties in which the two Yb^III 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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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

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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来源期刊

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.