[3,3']-[1,2-phenylenebis(iminomethylidyne)-bis(2,4-pentanedione)-N,N',O(2),O(2)'] | 40895-08-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [3,3']-[1,2-phenylenebis(iminomethylidyne)-bis(2,4-pentanedione)-N,N',O(2),O(2)']
• 英文别名: (3,3')-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedione)；[3,3']-[1,2-phenylenebis(iminomethylidyne)bis(2,4-pentanedione)]；1,2-bis-((2-acetyl-1-buten-3-on-1-yl)amino)benzene；1,2-bis(3-azomethinopentane-2,4-dione)-benzene；(C6H4)(NHCHC(COMe)C(O)CH3)2；3-[[2-[(2-acetyl-3-oxobut-1-enyl)amino]anilino]methylidene]pentane-2,4-dione
• CAS: 40895-08-7
• 化学式: C₁₈H₂₀N₂O₄
• mdl: MFCD07181143
• 分子量: 328.368
• InChiKey: MEDBNRHGDZZBLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.63
• 重原子数：
  24.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  92.34
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  [3,3']-[1,2-phenylenebis(iminomethylidyne)-bis(2,4-pentanedione)-N,N',O(2),O(2)'] 反应 168.0h， 生成 [FeL1(pina)]*2MeOH
  参考文献：
  名称：

  Large Thermal Hysteresis for Iron(II) Spin Crossover Complexes with N-(Pyrid-4-yl)isonicotinamide

  摘要：

  A new series of iron(II) 1D coordination polymers with the general formula [FeL1(pina)].xsolvent with L1 being a tetradentate N2O22- coordinating Schiff-base-like ligand [([3,3']-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2-)-N,N',O-2,O-2'], and pina being a bridging axial ligand N-(pyrid-4-yl)isonicotinamide, are discussed. The X-ray crystal structure of [FeL1(pina)].2MeOH was solved for the low-spin state. The compound crystallizes in the monoclinic space group P21/c, and the analysis of the crystal packing reveals the formation of a hydrogen bond network where additional methanol molecules are included. Different magnetic properties are observed for the seven samples analyzed, depending on the nature of the included solvent molecules. The widest hysteresis loop is observed for a fine crystalline sample of composition [FeL1(pina)].xH(2)O/MeOH. The 88 K wide thermal hysteresis loop (T1/2 up arrow = 328 K and T1/2 up arrow = 240 K) is centered around room temperature and can be repeated without of a loss of the spin transition properties. For the single crystals of [FeL1(pina)].2MeOH, a 51 K wide hysteresis loop is observed (T1/2 up arrow= 296 K and T1/2? = 245 K) that is also stable for several cycles. For a powder sample of [FeL1(pina)].0.5H2O.0.5MeOH a cooperative spin transition with a 46 K wide hysteresis loop around room temperature is observed (T1/2 up arrow = 321 K and T1/2 up arrow = 275 K). This compound was further investigated using Mossbauer spectroscopy and DSC. Both methods reveal that, in the cooling mode, the spin transition is accompanied by a phase transition while in the heating mode a loss of the included methanol is observed that leads to a loss of the spin transition properties. These results show that the pina ligand was used successfully in a crystal-engineering-like approach to generate 1D coordination polymers and improve their spin crossover properties.

  DOI：

  10.1021/ic501624b

文献信息

• Bis(cyclopentadienyl)titanium(IV)zirconium(IV) derivatives with jäger-type ligands
  作者：R. Rai、K.D. Mishra、O.P. Pandey、S.K. Sengupta

  DOI：10.1016/s0277-5387(00)83269-6

  日期：1992.1

  Bis(cyclopentadienyl)titanium(IV)/zirconium(IV) complexes, [Cp2M(J-R)] [where M = Ti or Zr and H2J-R is a Jäger type ligand with bridging group R (ethylene, o-phenylene or 4-methyl-o-phenylene], have been synthesized. The subsequent condensations of the complexes (R = o-phenylene) with o-phenylenediamine have also been studied, which cause ring closure and the formation of cyclic complexes. All these

  双（环戊二烯基）钛（IV）/锆（IV）配合物，[Cp 2 M（JR）] [其中M = Ti或Zr，H 2 J-R是带有桥基R（J，乙烯，邻-亚苯基或-）的Jäger型配体合成了[ 4-甲基-邻苯撑]，随后研究了配合物（R =邻苯撑）与邻苯二胺的缩合反应，这些反应会导致闭环和环状配合物的形成，所有这些衍生物都是通过元素分析，电导，磁矩和光谱（电子，IR，1 HNMR）的数据。1这些配合物的1 H NMR谱表明环戊二烯基环绕金属环轴快速旋转。提出了复合物的可能结构。
• Cooperative Iron(II) Spin Crossover Complexes with N₄O₂ Coordination Sphere
  作者：Birgit Weber、Eike Kaps、Jan Weigand、Chiara Carbonera、Jean-François Létard、Klaus Achterhold、Fritz G. Parak

  DOI：10.1021/ic070067o

  日期：2008.1.1

  Two new spin crossover complexes [FeL(py)(2)] (1) and [FeL(DMAP)(2)] (2) with L being a tetradentate N(2)O(2)(2-) coordinating Schiff-base-like ligand [([3,3']-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2-)-N,N',O(2 ),O(2)'], py = pyridine and DMAP = p-dimethylaminopyridine have been investigated using temperature-dependent susceptibility and thermogravimetric and photomagnetic measurements

  自旋转变之后还进行了不同的温度扫描量热法和Mossbauer光谱分析，得到了2，并且发现使用不同方法获得的转变温度有很好的一致性。X射线结构分析的结果表明，协同相互作用是由于两种化合物中的弹性相互作用而引起的。在2的情况下，它们的分子间铁-铁距离非常短，为7.2 A，并且发生了几次强烈的CC接触，这种现象更加明显。铁中心自旋态的变化伴随着O-Fe-O角（赤道配体的所谓位）的变化，从高自旋态的108度到低自旋态的90度。旋转状态。两种化合物在低温下的反射率测量结果表明，在样品表面发生了光诱导的激发自旋态俘获（LIESST）效应。在使用SQUID磁力计的整体条件下，复合物2表现出一些光磁特性，光激发水平为60％，T（LIESST）值为53 K.
• Synthesis and Characterisation of Two New Iron(II) Spin‐Crossover Complexes with N ₄ O ₂ Coordination Spheres – Optimizing Preconditions for Cooperative Interactions
  作者：Birgit Weber、Eike S. Kaps、Cedric Desplanches、Jean‐François Létard、Klaus Achterhold、Fritz G. Parak

  DOI：10.1002/ejic.200800420

  日期：2008.11

  E)-[diethyl 2,2′-[1,2-phenylenebis(iminomethylidyne)]bis(3-oxobutanoato)(2–)-N,N′,O3,O3′], L2 = [(3,3′)-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2–)-N,N′,O2,O2′]and phpy = 4-phenylpyridine} have been investigated using temperature-dependent susceptibility and photomagnetic measurements, as well as Mossbauer spectroscopy and X-ray structure analysis. Compound 1 shows a cooperative spin transition

  两个新的自旋交叉复合物，[FeL1(phpy)2] (1) 和 [FeL2(phpy)2](phpy) (2)，其中 L1 和 L2 是四齿 N2O22——配位 Schiff 碱样配体 L1 = (E,E)-[二乙基 2,2'-[1,2-亚苯基双(亚氨基亚甲基)]双(3-氧代丁酸)(2-)-N,N',O3,O3'], L2 = [( 3,3')-[1,2-亚苯基双(亚氨基甲基)]双(2,4-戊二酮)(2-)-N,N',O2,O2']和phpy = 4-苯基吡啶}已使用温度相关磁化率和光磁测量，以及穆斯堡尔光谱和 X 射线结构分析。化合物 1 显示了具有大约 4 K 宽的热滞回线（T1/2 = 232 K 和 T1/2 = 236 K）的协同自旋跃迁。2 的自旋跃迁是逐渐的，T1/2 ≈ 290 K。X射线结构分析结果表明，在1的情况下，协同相互作用是由于与几个强烈的C-C接触的弹性相互作
• Magnetic Ordering in Iron(II) Complexes due to a 2D Network of Hydrogen Bonds
  作者：Birgit Weber、Ernst-G. Jäger

  DOI：10.1002/zaac.200800338

  日期：2009.1

  The magnetic properties of two octahedral iron(II) complexes with Schiff base like equatorial N2O2 coordinating ligands and methanol (MeOH) as axial ligand are reported. Both compounds [FeL1(MeOH)2] (1) and [FeL2(MeOH)2] (2) (with L1 = [3,3′]-[1,2-phenylenebis(iminomethylidyne)-bis(2,4-pentanedionato)(2-)-N,N′,O2,O2′] and L2 = [E,E]-[diethyl 2,2′-1,2-phenylenebis(iminomethylidyne)bis(3-oxo-3-phenylpropanato)}

  报道了两个八面体铁 (II) 配合物与希夫碱如赤道 N2O2 配位配体和甲醇 (MeOH) 作为轴向配体的磁性。两种化合物 [FeL1(MeOH)2] (1) 和 [FeL2(MeOH)2] (2)（其中 L1 = [3,3']-[1,2-亚苯基双（亚氨基亚甲基）-双（2,4- pentanedionato)(2-)-N,N',O2,O2'] 和 L2 = [E,E]-[二乙基 2,2'-1,2-亚苯基双(亚氨基甲基亚基)双(3-oxo-3-苯基丙酸根)} (2-)-N,N',O3,O3']) 在 TC = 10 K 以下显示出微弱的自发磁化强度。 1 的 X 射线结构分析结果表明，这是由于氢的二维网络前面讨论过的类似复合物的键。
• Synthesis of Anionic Spin Crossover Complexes with Schiff Base like Ligands
  作者：Stephan Schlamp、Johanna Schulten、Richard Betz、Tobias Bauch、Anja Verena Mudring、Birgit Weber

  DOI：10.1002/zaac.201200162

  日期：2012.6

  The reaction of neutral iron(II) complexes of tetradentate Schiff base like ligands with the pseudohalogenides SCN–, OCN–, and CN– as monodentate axial ligands was investigated. In solution the formation of octahedral complexes could be confirmed and it was possible to follow a spin transition by T-dependent 1H NMR spectroscopy. In the solid only pentacoordinate complexes were obtained and the X-ray

  研究了四齿席夫碱样配体的中性铁 (II) 配合物与作为单齿轴向配体的拟卤化物 SCN-、OCN- 和 CN- 的反应。在溶液中，八面体配合物的形成可以得到证实，并且可以通过 T 依赖的 1H NMR 光谱跟踪自旋跃迁。在固体中只获得了五配位配合物，并讨论了五种单阴离子五配位铁 (II) 配合物和一个有趣的三核配合物的 X 射线结构。