Ancillary ligand modulated stereoselective self-assembly of triple-stranded Eu(iii) helicate featuring circularly polarized luminescence.
Ancillary ligand modulated stereoselective self-assembly of triple-stranded Eu(iii) helicate featuring circularly polarized luminescence.
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具有圆偏振发光特征的三链Eu(iii)螺旋的辅助配体调节立体选择性自组装
DOI：
10.1039/d1ra01583d
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发表时间：
2021-03-10
期刊：
影响因子：
3.9
通讯作者：
Li H
中科院分区：
文献类型：
--
作者：
Yao Z;Zhou Y;Gao T;Yan P;Li H
制备光学纯净的金属组装体是手性超分子领域的研究热点。合成了三个新的三链Eu(III)螺旋化合物Eu2L3(L‘)2[L=4，4′-bis(4，4，4-trifluoro-1，3-dioxobutyl)diphenyl硫化物；L’=1，10-菲咯啉(Phen)或R/S-2，2′-bis(diphenylphosphinyl)-1，1′-binaphthyl(R/S-BINAPO)]，以研究辅助配体对稀土螺旋结构立体选择性自组装的影响。X-射线单晶结构分析表明，Eu2L3(Phen)2为无手性空间群P1-̄，单胞内P和M螺旋酸盐的数量相当。分离得到的Eu2L3(S-BINAPO)2和Eu2L3(R-BINAPO)2经~1H、~(19)F、~(31)P核磁共振和剂量核磁共振确证为对映体。此外，镜像圆二色谱还证实了对映体的成功合成和从BINAPO到手性L的有效手性转变。此外，Eu2L3(S-BINAPO)2和Eu2L3(R-BINAPO)2的完美镜像圆偏振发光光谱表明，Eu3+中心存在与|glum|值相关的激发态手性，|glum|值达到0.112。此外，还讨论了三种螺旋的光物理性质。手性辅助配体(R/S-BINAPO)调控了稀土螺旋化合物的立体选择性自组装，表现出较强的发光性能，其GLUM|值高达0.112，发光量子产率高达34%。
Creating optically pure metal assemblies is a hot research topic in the realms of chiral supramolecules. Here, three new triple-stranded europium(iii) helicates Eu2L3(L′)2 [L = 4,4′-bis(4,4,4-trifluoro-1,3-dioxobutyl)diphenyl sulphide; L′ = 1,10-phenanthroline (Phen) or R/S-2,2′-bis(diphenylphosphinyl)-1,1′-binaphthyl (R/S-BINAPO)] were synthesized in order to investigate the effects of ancillary ligands on controlling the stereoselective self-assembly of lanthanide helicates. X-ray single crystal structure analysis showed that Eu2L3(Phen)2 crystalized in an achiral space group P1̄ with the equivalent amount of P and M helicates in one single cell. The isolated Eu2L3(S-BINAPO)2 and Eu2L3(R-BINAPO)2 were verified to be enantiopure by 1H, 19F, 31P NMR and DOSY NMR analyses. Additionally, the mirror-image CD spectra also demonstrated the successful syntheses of the enantiomers and the presence of an effective chirality transformation from BINAPO to achiral L. Furthermore, the perfect mirror-image circularly polarized luminescence (CPL) spectra of Eu2L3(S-BINAPO)2 and Eu2L3(R-BINAPO)2 indicated the existence of the excited state chirality of the Eu3+ center associated with |glum| values reaching 0.112. In addition, the photophysical properties of three helicates were also discussed. Chiral ancillary ligands (R/S-BINAPO) modulated the stereoselective self-assembly of lanthanide helicates, which presented strong CPL with |glum| values up to 0.112 and high luminescence quantum yield up to 34%.
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影响因子：
4.6
作者：
Barry, Dawn E.;Kitchen, Jonathan A.;Gunnlaugsson, Thorfinnur
通讯作者：
Gunnlaugsson, Thorfinnur
影响因子：
16.6
作者：
Imai, Yuki;Nakano, Yuka;Yuasa, Junpei
通讯作者：
Yuasa, Junpei
影响因子：
4
作者：
Barry, Dawn E.;Kitchen, Jonathan A.;Gunnlaugsson, Thorfinnur
通讯作者：
Gunnlaugsson, Thorfinnur
DOI：
10.1016/s0168-1273(96)23006-5
发表时间：
1996-01-01
期刊：
HANDBOOK ON THE PHYSICS AND CHEMISTRY OF RARE EARTHS, VOL 23
影响因子：
--
作者：
GorllerWalrand, C;Binnemans, K
通讯作者：
Binnemans, K
四链 Eu2L4 螺旋的预组织螺旋手性控制同手性自组装和圆偏振发光
影响因子：
4
作者：
Han, Guoying;Zhou, Yanyan;Yan, Pengfei
通讯作者：
Yan, Pengfei