Circularly polarized (CP) green-light of two chiral Zn(II)-Tb(III)-Salen heterobinuclear enantiomers

IF 3.3 3区物理与天体物理 Q2 OPTICS Journal of Luminescence Pub Date : 2024-08-31 DOI:10.1016/j.jlumin.2024.120871

Chenxi Shao , Youquan Chen , Zhiming Zhang , Siyu Hou , Yan Zhang , Guorui Fu , Jiaxiang Liu , Xingqiang Lü

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Abstract

Despite the appreciable high color-purity green-light of chiral Tb³⁺-complexes, it remains a great challenge to enable their both high quantum efficiency and large circularly polarized light (CPL) activity. Herein, through the self-assemble of the chiral Salen-type bis-Schiff-base ligand (S,S)-H₂L or (R,R)-H₂L with Zn(OAc)₂·2H₂O and Ln (NO₃)₃·6H₂O (Ln = La, Tb, Gd), two series of chiral Zn(II)-Ln (III)-heterobinuclear enantiomers [Zn ((S,S)-L)Ln (μ₁-OAc)(μ₂-NO₃)₂] (Ln = La, 1; Tb, 2; Gd, 3) or [Zn ((R,R)-L)Ln (μ₁-OAc)(μ₂-NO₃)₂] (Ln = La, 4; Tb, 5; Gd, 6) were afforded, respectively. Photophysical study shows that the destabilized ³π-π* energy level upon Zn²⁺ coordination, is confirmed to effectively sensitize of the Tb³⁺-centered green-light for the two chiral complexes [Zn ((S,S)-L)Tb (μ₁-OAc)(μ₂-NO₃)₂] (2) and [Zn ((R,R)-L)Tb (μ₁-OAc)(μ₂-NO₃)₂] (5). The merits of efficient ( $Φ_{Tb}^{L}$ = 5.6–6.2 %) Tb³⁺-centered green-light and strong CPL activity (|g_PL| = 0.03, ⁵D₄→⁷F₃ transition), engender chiral Zn(II)-Tb(III)-Salen complexes like 2 and 5 a new platform to ideal chiral organo-Tb³⁺ candidates.

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两种手性 Zn(II)-Tb(III)-Salen 异核对映体的圆偏振 (CP) 绿光

尽管手性 Tb3+ 复合物可发出高色纯绿光，但要使其同时具有高量子效率和大圆偏振光（CPL）活性仍是一项巨大挑战。在此，通过手性萨伦型双希夫碱配体 (S,S)-H2L 或 (R,R)-H2L 与 Zn(OAc)2-2H2O 和 Ln (NO3)3-6H2O （Ln = La、Tb，Gd）、两个系列的手性 Zn（II）-Ln（III）-异核对映体[Zn（（S，S）-L）Ln（μ1-OAc）（μ2-NO3）2]（Ln = La，1；分别得到了[Zn ((R,R)-L)Ln (μ1-OAc)(μ2-NO3)2] (Ln = La, 1; Tb, 2; Gd, 3)或[Zn ((R,R)-L)Ln (μ1-OAc)(μ2-NO3)2] (Ln = La, 4; Tb, 5; Gd, 6)]。光物理研究表明，Zn2+配位后的不稳定 3π-π* 能级被证实能有效敏化以 Tb3+ 为中心的绿光，这两种手性配合物分别为[Zn ((S,S)-L)Tb (μ1-OAc)(μ2-NO3)2] (2)和[Zn ((R,R)-L)Tb (μ1-OAc)(μ2-NO3)2] (5)。高效（ΦTbL = 5.6-6.2 %）的以 Tb3+ 为中心的绿光和强大的 CPL 活性（|gPL| = 0.03，5D4→7F3 转变）等优点使 2 和 5 等手性 Zn(II)-Tb(III)-Salen 配合物成为理想的手性有机 Tb3+ 候选物的新平台。

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来源期刊

Journal of Luminescence 物理-光学

CiteScore

6.70

自引率

13.90%

发文量

850

审稿时长

3.8 months

期刊介绍： The purpose of the Journal of Luminescence is to provide a means of communication between scientists in different disciplines who share a common interest in the electronic excited states of molecular, ionic and covalent systems, whether crystalline, amorphous, or liquid. We invite original papers and reviews on such subjects as: exciton and polariton dynamics, dynamics of localized excited states, energy and charge transport in ordered and disordered systems, radiative and non-radiative recombination, relaxation processes, vibronic interactions in electronic excited states, photochemistry in condensed systems, excited state resonance, double resonance, spin dynamics, selective excitation spectroscopy, hole burning, coherent processes in excited states, (e.g. coherent optical transients, photon echoes, transient gratings), multiphoton processes, optical bistability, photochromism, and new techniques for the study of excited states. This list is not intended to be exhaustive. Papers in the traditional areas of optical spectroscopy (absorption, MCD, luminescence, Raman scattering) are welcome. Papers on applications (phosphors, scintillators, electro- and cathodo-luminescence, radiography, bioimaging, solar energy, energy conversion, etc.) are also welcome if they present results of scientific, rather than only technological interest. However, papers containing purely theoretical results, not related to phenomena in the excited states, as well as papers using luminescence spectroscopy to perform routine analytical chemistry or biochemistry procedures, are outside the scope of the journal. Some exceptions will be possible at the discretion of the editors.