(8-quinolyl)-5-nitrosalicylaldimine | 202277-66-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: (8-quinolyl)-5-nitrosalicylaldimine
• 英文别名: 4-nitro-2-((quinolin-8-ylimino)methyl)phenol；4-Nitro-2-(quinolin-8-yliminomethyl)-phenol；4-nitro-2-(quinolin-8-yliminomethyl)phenol
• CAS: 202277-66-5
• 化学式: C₁₆H₁₁N₃O₃
• 分子量: 293.282
• InChiKey: HTTIIADQECIAKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  iron(II) tetrafluoroborate hexahydrate 、 (8-quinolyl)-5-nitrosalicylaldimine 在 三乙胺 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 96.0h， 生成 Fe^II(qsal-5NO₂)₂
  参考文献：
  名称：

  Fe^II(pap-5NO₂)₂and Fe^II(qsal-5NO₂)₂Schiff-Base Spin-Crossover Complexes: A Rare Example with Photomagnetism and Room-Temperature Bistability

  摘要：

  We focus here on the properties of Fe complexes formed with Schiff bases involved in the chemistry of FeIII spin-transition archetypes. The neutral Fe(pap-5NO(2))(2) (1) and Fe(qsal-5NO(2))(2).Solv (2 and 2.Solv) compounds (Solv = 2H(2)O) derive from the reaction of FeII salts with the condensation products of pyridine-2-carbaldehyde with 2-hydroxy-5-nitroaniline (Hpap-5NO(2)) or 5-nitrosalicylaldehyde with quinolin-8-amine (Hqsal-5NO(2)), respectively. While the Fe(qsal-5NO(2))(2).Solv solid is essentially low spin (S = 0) and requires temperatures above 300 K to undergo a S = 0 <-> S = 2 spin-state switching, the Fe(pap-5NO(2))(2) one presents a strongly cooperative first-order transition (T-down arrow = 291 K, T? = 308 K) centered at room temperature associated with a photomagnetic effect at 10 K (TLIESST = 58 K). The investigation of these magnetic behaviors was conducted with single-crystal X-ray diffraction (1, 100 and 320 K; 2, 100 K), Mossbauer, IR, UVvis (1 and 2.Solv), and differential scanning calorimetry (1) measurements. The Mossbauer analysis supports a description of these compounds as FeII Schiff-base complexes and the occurrence of a metal-centered spin crossover process. In comparison with FeIII analogues, it appears that an expanded coordination sphere stabilizes the valence 2+ state of the Fe ion in both complexes. Strong hydrogen-bonding interactions that implicate the phenolato group bound to FeII promote the required extra-stabilization of the S = 2 state and thus determines the spin transition of 1 centered at room temperature. In the lattice, the hydrogen-bonded sites form infinite chains interconnected via a three-dimensional network of intermolecular van der Waals contacts and pp interactions. Therefore, the spin transition of 1 involves the synergetic influence of electrostatic and elastic interactions, which cause the enhancement of cooperativity and result in the bistability at room temperature.

  DOI：

  10.1021/ic5027043
• 作为产物：
  描述：

  8-氨基喹啉 、 5-硝基水杨醛 以 甲醇 为溶剂， 反应 3.0h， 以87%的产率得到(8-quinolyl)-5-nitrosalicylaldimine
  参考文献：
  名称：

  The development of two fluorescent chemosensors for the selective detection of Zn²⁺ and Al³⁺ ions in a quinoline platform by tuning the substituents in the receptor part: elucidation of the structures of the metal-bound chemosensors and biological studies

  摘要：

  报道了两种基于氨基喹啉的化学传感器（HL1和HL2），用于选择性检测Zn2+和Al3+离子。

  DOI：

  10.1039/c9dt04902a

文献信息

• Fluorescent Tin(IV) Complexes with Schiff Base Ligands
  作者：Kentaro Takano、Takashi Shibahara

  DOI：10.1246/cl.2008.70

  日期：2008.1.5

  Five novel fluorescent Schiff base tin(IV) complexes of the type [SnCl3(L)] were synthesized and their properties were investigated: the emission wavelengths range from bluish green to orange (λmax: 492–545 nm). DFT calculation shows that the order of the magnitudes of HOMO–LUMO gaps is consonant with that of the emission wavelengths (λmax) of the complexes, and good correlation was observed between reduction potentials in DMSO and the energies of LUMO.

  合成了五种新型荧光席夫碱锡(IV)配合物，其类型为[SnCl₃(L)]，并研究了它们的性质：这些配合物的最大发射波长范围从蓝绿色到橙色（λmax：492-545 nm）。DFT计算表明，最高占据分子轨道（HOMO）与最低未占据分子轨道（LUMO）之间的能隙大小顺序与配合物的最大发射波长（λmax）顺序一致，在二甲基亚砜(DMSO)中观察到了还原电位与LUMO能级之间的良好相关性。
• Fluorescent Tin(IV) Complexes with Schiff Base Ligands: Synthesis, Structures, and Fluorescence Lifetime
  作者：Kentaro Takano、Masayuki Takahashi、Takaaki Fukushima、Makoto Takezaki、Toshihiro Tominaga、Haruo Akashi、Hideaki Takagi、Takashi Shibahara

  DOI：10.1246/bcsj.20120150

  日期：2012.11.15

  Eleven Schiff base tin(IV) complexes of the type [SnCl3(L)] (HL: Schiff base) were synthesized and structurally characterized by X-ray crystallography and 1H NMR spectroscopy, and their properties were investigated. The Schiff bases are prepared from aldehydes with a benzene or a naphthalene ring and 8-aminoquinoline or its derivatives. The complexes adopt geometries close to octahedral, with three chloride ions coordinated meridionally. Eight of the eleven tin complexes show fluorescence in DMSO, and the emission range from bluish green to orange (λmax: 492–545 nm). Two solid tin complexes are fluorescent, although they are not in DMSO, and one tin complex is not fluorescent even in the solid state. The fluorescence quantum yields (Φf) of the complexes depend very much on the ligands (Φf = 0.21–0.022). The fluorescence lifetimes (τ = 0.49–1.76 ns) were measured and the results will be discussed. DFT calculation (B3LYP/Sn, LanL2DZ; others, 6-31G**) shows that the order of the magnitudes of HOMO–LUMO gaps is consonant with that of the emission wavelengths (λmax) of the complexes. All the cyclic voltammograms of the Schiff base ligands and the complexes exhibited irreversible waves and these results suggest that the reduction products of the ligands and the complexes were unstable under the time scale in CV measurements (0.1 V s−1). Relatively good correlation was observed between reduction potentials in DMSO and the energies of LUMO.

  通过 X 射线晶体学和 1H NMR 光谱法合成了 11 种 [SnCl3(L)] 型锡（IV）希夫碱配合物（HL：希夫碱），并对其结构和性质进行了表征和研究。希夫碱由带有苯环或萘环的醛和 8-氨基喹啉或其衍生物制备而成。这些络合物采用接近八面体的几何结构，三个氯离子在经阴离子上配位。11 种锡络合物中有 8 种在二甲基亚砜中显示荧光，发射范围从蓝绿色到橙色（λmax：492-545 nm）。两种固态锡络合物虽然在二甲基亚砜中没有荧光，但也有荧光，一种锡络合物即使在固态下也没有荧光。配合物的荧光量子产率（Φf）在很大程度上取决于配体（Φf = 0.21-0.022）。对荧光寿命（τ = 0.49-1.76 ns）进行了测量，并将对结果进行讨论。DFT 计算（B3LYP/Sn，LanL2DZ；其他，6-31G**）表明，HOMO-LUMO 间隙的大小顺序与配合物的发射波长（λmax）一致。希夫碱配体和配合物的所有循环伏安图都显示出不可逆波，这些结果表明配体和配合物的还原产物在循环伏安测量的时间尺度（0.1 V s-1）下是不稳定的。在 DMSO 中观察到的还原电位与 LUMO 的能量之间存在较好的相关性。
• Fe^II(pap-5NO₂)₂and Fe^II(qsal-5NO₂)₂Schiff-Base Spin-Crossover Complexes: A Rare Example with Photomagnetism and Room-Temperature Bistability
  作者：Olga Iasco、Eric Rivière、Régis Guillot、Marylise Buron-Le Cointe、Jean-François Meunier、Azzedine Bousseksou、Marie-Laure Boillot

  DOI：10.1021/ic5027043

  日期：2015.2.16

  We focus here on the properties of Fe complexes formed with Schiff bases involved in the chemistry of FeIII spin-transition archetypes. The neutral Fe(pap-5NO(2))(2) (1) and Fe(qsal-5NO(2))(2).Solv (2 and 2.Solv) compounds (Solv = 2H(2)O) derive from the reaction of FeII salts with the condensation products of pyridine-2-carbaldehyde with 2-hydroxy-5-nitroaniline (Hpap-5NO(2)) or 5-nitrosalicylaldehyde with quinolin-8-amine (Hqsal-5NO(2)), respectively. While the Fe(qsal-5NO(2))(2).Solv solid is essentially low spin (S = 0) and requires temperatures above 300 K to undergo a S = 0 <-> S = 2 spin-state switching, the Fe(pap-5NO(2))(2) one presents a strongly cooperative first-order transition (T-down arrow = 291 K, T? = 308 K) centered at room temperature associated with a photomagnetic effect at 10 K (TLIESST = 58 K). The investigation of these magnetic behaviors was conducted with single-crystal X-ray diffraction (1, 100 and 320 K; 2, 100 K), Mossbauer, IR, UVvis (1 and 2.Solv), and differential scanning calorimetry (1) measurements. The Mossbauer analysis supports a description of these compounds as FeII Schiff-base complexes and the occurrence of a metal-centered spin crossover process. In comparison with FeIII analogues, it appears that an expanded coordination sphere stabilizes the valence 2+ state of the Fe ion in both complexes. Strong hydrogen-bonding interactions that implicate the phenolato group bound to FeII promote the required extra-stabilization of the S = 2 state and thus determines the spin transition of 1 centered at room temperature. In the lattice, the hydrogen-bonded sites form infinite chains interconnected via a three-dimensional network of intermolecular van der Waals contacts and pp interactions. Therefore, the spin transition of 1 involves the synergetic influence of electrostatic and elastic interactions, which cause the enhancement of cooperativity and result in the bistability at room temperature.
• The development of two fluorescent chemosensors for the selective detection of Zn²⁺ and Al³⁺ ions in a quinoline platform by tuning the substituents in the receptor part: elucidation of the structures of the metal-bound chemosensors and biological studies
  作者：Pravat Ghorai、Kunal Pal、Parimal Karmakar、Amrita Saha

  DOI：10.1039/c9dt04902a

  日期：——

  Two aminoquinoline-based chemosensors (HL1 and HL2) are reported for selective detection of Zn²⁺ and Al³⁺ ions.

  报道了两种基于氨基喹啉的化学传感器（HL1和HL2），用于选择性检测Zn2+和Al3+离子。