[EuCl2(2,2'-bipyridine)(H2O)4]Cl*H2O | 249609-05-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [EuCl2(2,2'-bipyridine)(H2O)4]Cl*H2O
• 英文别名: [EuCl2(bpy)(H2O)4]Cl*H2O；europium(3+);2-pyridin-2-ylpyridine;trichloride;pentahydrate
• CAS: 249609-05-0
• 化学式: C₁₀H₁₆Cl₂EuN₂O₄*Cl*H₂O
• 分子量: 504.582
• InChiKey: QTAIVFMHZJCNKX-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -10.97
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  30.8
• 氢给体数：
  5
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  2,2'-联吡啶 、 europium(III) chloride hexahydrate 以 水 为溶剂， 生成 [EuCl2(2,2'-bipyridine)(H2O)4]Cl*H2O
  参考文献：
  名称：

  Structural Systematics of Rare Earth Complexes. XVIII (Hydrated) Mononuclear 1 : 1 Adducts of Lanthanoid(III) Chlorides with 2,2′-Bipyridine

  摘要：

  本研究记录了水合镧系元素（III）氯化物与 2,2′-联吡啶（"bpy"）的一些加合物的室温单晶 X 射线结构测定结果，这些加合物是从水/乙醇溶液中结晶出来的，其中含有单核阵列，其 Ln/bpy 的化学计量为 1:1。与 Ln 系列重金属有关的扩展同构系列已经确定：LnCl3/bpy/H2O（1 : 1 ：6)（[(bpy)Ln(OH2)6]Cl3），似乎（至少）包括 Ln = Ho(-)Lu 和 Y 的范围，是单斜晶体，P 21/n，a ≈ 14-2，b ≈ 7-7，c ≈ 17-4 Å，β ≈ 91°，Z = 4，具有八坐标 LnN2O6 阵列；对于第 2435、3120、1846 个独立的 "观察到的"（I > 3σ(I)）衍射仪反射（Ln = Ho、Lu、Y），|F|上的常规 R 值分别为 0-043、0-029、0-057。LnCl3/bpy/H2O (1 : 1-5 : 8) 的晶体（[(bpy)Ln(OH2)6]Cl3.½bpy.2H2O），似乎（至少）包括 Ln = Er(-)Lu 和 Y 的范围，呈三菱形，P 1，a ≈ 11-7，b ≈ 11-0，c ≈ 10-1 Å，α ≈ 85-8、β≈74-7，γ≈79-5°，Z = 2，R 0-038，0-033，0-048，No 3897，4377，3130，与 HoCl3/bpy/H2O（1 ：2：7）、[(镱)Ho(OH2)6]Cl3。bpy.H2O，正交，Pbca，a 18-02(2)，b 20-06(2)，c 15-051(9)埃，Z = 8，R 0-057，为 No 3009。相比之下，迄今为止，在较轻的镧系元素中只发现了零星、多样和不相关的形式：EuCl3/bpy/H2O(1 : 1 : 5) ([(bpy)Eu(OH2)4Cl2]Cl.H2O)，三菱形，P 1，a 11-506(7)，b 11-098(5)，c 6-974(8)埃，α 77-35(7)，b 85-1(1)，γ 89-54(4)°，Z = 2，R 0-063 为 No 4633，还包含一个单核[(N,N′-bidentate)Ln(unidentate)6]阵列。PrCl3/bpy/H2O(1 : 1 : 3)(×4)是一种特殊的化合物，为 2[(bpy)Pr(OH2)3Cl3] [(bpy)(H2O)2Cl2Pr(µ-Cl)2PrCl2(OH2)2(bpy)]。2H2O，三菱形，P 1，a 13-490(4)，b 11-121(2)，c 10-162(1)埃，α 96-06(1)，β 90-08(2)，γ 96-43(2)°，Z = 2 f.u、R 0-045 表示 No 4127，其单核种类的配比为 PrCl3/bpy/H2O（1:1:3），双核种类的配比为 1:1:2。双核乙醇溶解阵列的特征是 LaCl3/bpy/EtOH (1 : 1 ：2）[(bpy)(EtOH)2Cl2La(µ-Cl)2LaCl2(HOEt)2(bpy)]，具有八配位镧；该配合物为三菱形，P 1，a 11-426(8)，b 10-673(7)，c 10-453(7)埃，α 109-60(5)，β 113-10(5)，γ 105-80(5)°，Z = 1 二聚体，R 0-046 为 No 2786。

  DOI：

  10.1071/ch98049

文献信息

• Intermolecular Interactions as Actors in Energy-Transfer Processes in Lanthanide Complexes with 2,2′-Bipyridine
  作者：Lada N. Puntus、Konstantin A. Lyssenko、Irina S. Pekareva、Jean-Claude G. Bünzli

  DOI：10.1021/jp902390z

  日期：2009.7.9

  A series of lanthanide complexes [LnCl(x)(bpy)(y)(H2O)(z)]-Cl-3-(x)(H2O)(n)(EtOH)(m) (Ln = Eu, Gd, Tb; x = 1, 2; y = 1, 2; z = 2-4) with different numbers of 2,2'-bipyridine (bpy), chloride ions, and water molecules in the inner coordination sphere were synthesized and investigated with the aim of relating their molecular geometry and crystal packing to the efficiency of ligand-to-metal energy transfer. In conjunction to the rotation of the pyridine rings upon coordination to the Ln ion, the high flexibility displayed by bpy ligands leads to rather unexpected bending of these rings with respect to the central bond, owing to intermolecular interactions such as Cl center dot center dot center dot pi and pi-stacking ones. Deciphering the luminescence properties of the Eu and Tb complexes needs to take into account both the composition of the inner coordination sphere and the peculiarities of the crystal packing. For instance, in addition to the classical ligand -> Eu charge-transfer state (LMCT), another charge-transfer state induced by pi-stacking interactions (SICT) could be identified. These two states, located between the singlet and triplet states of the bpy ligand(s), provide relays facilitating the energy migration from the singlet to the triplet states and eventually to the excited Eu states, improving the overall ligand-to-Eu energy transfer. Another point is the involvement of the inner-sphere water molecules in H-bonding with chloride ions, which considerably lowers their luminescence quenching ability, so that the adducts remain highly luminescent. For instance, the terbium chloride with two bpy ligands is an efficient near-UV to green light converter, with an overall quantum yield equal to 37% despite the coordinated water molecules. The interpretations given are substantiated by DFT and TD-DFr theoretical calculations of the complexes and ligand assemblies.