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Chiral supramolecular assemblies for second-order nonlinear optics and chiral sensing.

机译:用于二阶非线性光学和手性传感的手性超分子组件。

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摘要

Three novel NLO materials: bis{lcub}4-[2-(4-pyridyl)ethenyl]benzoato{rcub}-zinc (II) and -cadmium(II) with 8-fold diamondoid network structures along with octupolar [Cd3(□3-OH)(4-[2-(4-pyridyl)ethenyl]benzoato) 3(py)6](ClO4)2, have been synthesized under hydro(solvo)thermal conditions and exhibit powder second harmonic generation efficiencies comparable to that of technologically important lithium niobate.; One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate) 3(H2O)2 (Ln = Ce, Pr, Nd, Sm, Eu, and Tb, 1a–1f) were synthesized under hydro(solvo)thermal conditions. Single crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate) 2-Ln and Ln-(carboxylate)4-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite chain structure with one chelating carboxylate group on each metal center. Tb(isonicotinate) 3(H2O)2 is highly emissive at room temperature with a quantum yield of ∼90%.; A series of well-defined optically active 1,1-binaphthyl-based oligomers, linked through their 6,6-positions that range from tetranaphthol to decanaphthol, have been synthesized. A combination of X-ray structural and CD studies suggests that these oligonaphthyls adopt zig-zag, but not helical conformation. As the chain length increases, these oligomers exhibit the enhanced fluorescence, which can be quenched very efficiently by chiral 1,2-diaminocyclohexane. Most interestingly, the fluorescence of hexanaphthol can be quenched enantioselectively by 1,2-diaminocyclohexane with a selectivity of 1.24. The present work thus demonstrates the potential of constructing chiral sensory materials based on well-defined enantiopure oligonaphthols.; Optically active dendrimers containing a 1,1-binaphthyl core and its oligomer core were synthesized. The chiral optical properties were also studied by UV, fluorescence, optical rotation and CD spectra.
机译:三种新颖的NLO材料:双{lcub} 4- [2-(4-吡啶基)乙烯基]苯并(rcub}-锌(II)和-镉(II),具有八倍的类金刚石网络结构以及八极[Cd 3 (□ 3 -OH)(4- [2-(4-吡啶基)乙烯基]苯并) 3 (py) 6 ](ClO 4 2 ,是在水(溶剂)热条件下合成的,具有与技术上重要的铌酸锂相当的粉末二次谐波产生效率。 。;分子式为Ln(异烟酸) 3 (H 2 O) 2 的一维镧系配位聚合物(Ln = Ce,Pr,Nd,在水(溶剂)热条件下合成了Sm,Eu和Tb, 1a-1f )。单晶和粉末X射线衍射研究表明,这些镧系配位聚合物采用两种不同的结构。 Ce(III),Pr(III)和Nd(III)配合物采用的链结构具有交替的Ln-(羧酸盐) 2 -Ln和Ln-(羧酸盐) 4 -Ln键,Sm(III),Eu(III)和Tb(III)配合物具有双羧基桥接的无限链结构,每个金属中心均具有一个螯合的羧基。 Tb(异烟酸) 3 (H 2 O) 2 在室温下具有高发射率,量子产率约为90%。一系列定义明确的旋光的1,1 '-联萘基低聚物,通过它们从6,萘酚到十萘酚的6,6 '-位连接在一起,合成的。 X射线结构和CD研究的结合表明,这些寡萘基采用锯齿形而不是螺旋形构象。随着链长的增加,这些低聚物显示出增强的荧光,可以通过手性1,2-二氨基环己烷非常有效地猝灭。最有趣的是,可以通过1,2-二氨基环己烷以1.24的选择性对映体猝灭六萘酚的荧光。因此,本工作证明了基于定义明确的对映纯低聚酚的手性感觉材料的潜力。合成了含有1,1'super'-联萘核及其低聚物核的旋光树枝状聚合物。还通过紫外,荧光,旋光和CD光谱研究了手性光学性质。

著录项

  • 作者

    Ma, Ling.;

  • 作者单位

    Brandeis University.;

  • 授予单位 Brandeis University.;
  • 学科 Chemistry Organic.; Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2002
  • 页码 116 p.
  • 总页数 116
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;无机化学;
  • 关键词

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