天然(+)-樟脑基双(吡唑基)吡啶铕(III)配合物的区域异构体诱导圆极化发光开关

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Justin Cado, Alexandre Abhervé*, Maxime Grasser, Nicolas Vanthuyne, Francesco Zinna, Lorenzo Di Bari, Boris Le Guennic* and Narcis Avarvari*, 
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引用次数: 0

摘要

含有樟脑单元的手性2,6-二(吡唑-1-酰基)吡啶(bpp)配体已被用于制备发光铕(III)配合物的对映纯、外消旋和介体形式。bpp配体的单晶x射线衍射和热辐射光谱已被充分表征。对于其中一种对映纯配体,即his (4S,7R)樟脑-2,2-bpp,得到了含有一个通过N1氮原子连接的吡唑的区域异构体his (4S,7R)樟脑-1,2-bpp,并用于配位铕(III)离子。用辅助的六氟乙酰丙酮配体完成镧系元素的配位球。用单晶x射线衍射对2,2-bpp配合物进行了结构表征。对映纯化合物具有非中心对称的单斜P21空间群,中消旋体和外消旋体具有中心对称的单斜P21/n空间群。金属中心在轻微扭曲的松饼式几何结构中进行了enena协调。在7F1←5D0磁偶极子敏感跃迁中,三种对映物表现出较强的圆极化发光活性,各向异性因子glum达到±0.2。最值得注意的是,两个具有区域异构体his (4S,7R)樟脑-2,2-bpp和his (4S,7R)樟脑-1,2-bpp的配合物的发射极化是相反的,但具有相同的樟脑单元的绝对构型,从而允许前所未有的CPL切换的可能性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Regioisomerism Induced Circularly Polarized Luminescence Switching in Natural (+)-Camphor-Based Bis(pyrazolyl)pyridine Europium(III) Complexes

Regioisomerism Induced Circularly Polarized Luminescence Switching in Natural (+)-Camphor-Based Bis(pyrazolyl)pyridine Europium(III) Complexes

Regioisomerism Induced Circularly Polarized Luminescence Switching in Natural (+)-Camphor-Based Bis(pyrazolyl)pyridine Europium(III) Complexes

Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by single-crystal X-ray diffraction and chiroptical spectroscopy. For one of the enantiopure ligands, namely bis(4S,7R)camphor-2,2-bpp, the regioisomer bis(4S,7R)camphor-1,2-bpp, containing one pyrazole connected through the N1 nitrogen atom, has been obtained and used to coordinate the europium(III) ion. Ancillary hexafluoroacetylacetonato ligands were used to complete the coordination sphere of the lanthanide. The complexes with the 2,2-bpp ligands have been structurally characterized by single-crystal X-ray diffraction. They are isostructural in spite of the noncentrosymmetric monoclinic P21 space group for the enantiopure compounds and the centrosymmetric monoclinic P21/n space group for the meso and the racemic ones. The metal center is ennea-coordinated within slightly distorted Muffin-type geometry. The three enantiopure complexes show strong circularly polarized luminescence activity, with anisotropy factors glum reaching up ±0.2 for the 7F15D0 magnetic dipole sensitive transition. Most remarkably, the polarization of the emission is inverted for the two complexes bearing the regioisomeric bis(4S,7R)camphor-2,2-bpp and bis(4S,7R)camphor-1,2-bpp ligands, yet having the same absolute configuration of the camphor units, thus allowing an unprecedented possibility of CPL switching.

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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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