[IrCl(ppz)₂]₂

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [IrCl(ppz)₂]₂
• 英文别名: Chloroiridium(2+);1-phenylpyrazole
• 化学式: C₃₆H₂₈Cl₂Ir₂N₈
• 分子量: 1028.02
• InChiKey: FYHIZGVZTWWQAS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.06
• 重原子数：
  48
• 可旋转键数：
  4
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  71.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,7-二氯-8-羟基喹哪啶 、 [IrCl(ppz)₂]₂ 以 甲醇 、 二氯甲烷 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  环状金属化的Ir（III）-8-氧代胆碱络合物，用作特定线粒体成像和抗癌药物的红色探针

  摘要：

  一类新的发光Ir III抗肿瘤药，即[Ir（CP1）（PY1）2 ]（Ir-1），[Ir（CP1）（PY2）2 ]（Ir-2），[Ir（CP1）（ PY4）2 ]（Ir-3），[Ir（CP2）（PY1）2 ]（Ir-4），[Ir（CP2）（PY4）2 ]（Ir-5），[Ir（CP3）（PY1）2 ]⋅CH 3 OH（铱6），物[Ir（CP4）（PY4）2 ]⋅CH 3 OH（铱7），物[Ir（CP5）（PY2）2 ]（铱8），的[Ir （CP5）（PY4）2 ]⋅CH 3 OH（Ir-9），[Ir（CP6）（PY1）2 ]（Ir-10），[Ir（CP6）（PY2 ）2 ]·CH 3 OH（Ir-11），[Ir（CP6）（PY3）2 ]（Ir-12），[Ir（CP6）（PY41）2 ]（Ir-13）和[Ir（CP7）（PY1）2 ]（Ir-14），由8-氧代喹啉衍生物和1-苯基吡唑支撑制备了配体。与SK-OV-3

  DOI：

  10.1016/j.ejmech.2020.112192
• 作为产物：
  描述：

  iridium(III) chloride trihydrate 、 1-苯基吡唑 在 potassium carbonate 作用下， 以 乙二醇乙醚 为溶剂， 反应 24.0h， 生成 [IrCl(ppz)₂]₂
  参考文献：
  名称：

  桥联二芳基酰肼配体的双核环金属化铱（III）配合物的合成，非对映体分离及其光电和结构性质

  摘要：

  A series of diiridium complexes 13-16 bridged by diarylhydrazine ligands and cyclometalated by phenyl pyridine or phenylpyrazole ligands was synthesized. In all cases the Lambda Delta meso and Lambda Lambda/Delta Delta rac diastereomers were separated and characterized by single-crystal X-ray diffraction, revealing intramolecular pi-pi stacking between arenes of the bridging and cydometalating ligands. Density functional theory (DFT) calculations show that in general the HOMOs are mainly localized on the iridium centers, the cydometalating phenyl moieties, and the central hydrazide components of the bridging ligands, while the LUMOs are primarily localized on the N-heterocycles (pyridine or pyrazole) of the cydometalating ligands. This series of complexes, especially with the separated diastereomers, provides an ideal opportunity to study the effects of subtle structural changes on the optoelectronic properties of diiridium systems: significant differences are observed between the rdc and meso isomers in some cases. A cyclic voltammetric study of the electrochemical properties of the eight complexes reveals strong intramolecular interactions between the iridium centers. The photophysical properties are reported in solution and in rigid poly(methyl methacrylate) (PMMA) and 2-methyltetrahydrofuran (2-MeTHF) (at 77 K) matrices, where some of the complexes are strongly emissive in the turquoise and green regions (Phi(pL) = 42-68 +/- 10%) due to matrix-induced restricted intramolecular motion (RIM).

  DOI：

  10.1021/acs.organomet.6b00887

文献信息

• Elucidating the Origin of Enhanced Phosphorescence Emission in the Solid State (EPESS) in Cyclometallated Iridium Complexes
  作者：Ashlee J. Howarth、Raissa Patia、David L. Davies、Francesco Lelj、Michael O. Wolf、Kuldip Singh

  DOI：10.1002/ejic.201402495

  日期：2014.8

  A new mechanism for enhanced phosphorescence emission in the solid state (EPESS) in cyclometallated Ir complexes with the general formula [Ir(CN)2(NO)] involving distortion of the six-membered chelate ring of the ancillary ligand is proposed. Photophysical and computational studies show that neither π-stacking nor restricted rotation cause the observed EPESS in these complexes and that ligand distortions

  提出了一种在具有通式 [Ir(CN)2(NO)] 的环金属化 Ir 配合物中增强固态磷光发射 (EPESS) 的新机制，涉及辅助配体的六元螯合环的变形。光物理和计算研究表明，在这些配合物中观察到的 EPESS 既不是 π 堆积也不是限制旋转，并且三重激发态的配体畸变是 EPESS 的原因
• Photophysical behaviour of cyclometalated iridium(iii) complexes with phosphino(terthiophene) ligands
  作者：Stephanie A. Moore、David L. Davies、Marcus M. Karim、Jeffrey K. Nagle、Michael O. Wolf、Brian O. Patrick

  DOI：10.1039/c3dt51320c

  日期：——

  new IrIII complexes containing the 3′-phosphino-2,2′:5′,2′′-terthiophene (PT3) ligand in three different coordination modes are reported. The electronic properties of the complexes are characterized by cyclic voltammetry, absorption, emission and time-resolved transient absorption spectroscopies and DFT/TDDFT calculations. The electrochemical and photophysical behaviour of the complexes was found to

  报道了六种新的Ir III配合物，它们以三种不同的配位方式包含3'-膦基2,2'：5'，2''-噻吩（PT 3）配体。配合物的电子性质通过循环伏安法，吸收，发射和时间分辨的瞬态吸收光谱法以及DFT / TDDFT计算来表征。发现配合物的电化学和光物理行为受PT 3配体支配。对于PT 3配体以双齿P，S或P，C模式配位的配合物，最低的能量吸收带归因于π–π * PT 3与DFT计算得出的观察结果一致的局部过渡。在所有情况下，发射量子产率都很低（<0.07），发射寿命很短（<50 ns）。系统间交叉会导致长寿命的三重态（3 L），该状态也位于PT 3组上。在仅通过膦配位的PT 3配体的配合物中，TDDFT计算表明，在最低能量跃迁中具有MLCT（和Cl-PT 3 CT）特征。
• Complete Monitoring of Coherent and Incoherent Spin Flip Domains in the Recombination of Charge-Separated States of Donor-Iridium Complex-Acceptor Triads
  作者：Johannes H. Klein、David Schmidt、Ulrich E. Steiner、Christoph Lambert

  DOI：10.1021/jacs.5b04868

  日期：2015.9.2

  The spin chemistry of photoinduced charge-separated (CS) states of three triads comprising one or two triarylamine donors, a cyclometalated iridium complex sensitizer and a naphthalene diimide (NDI) acceptor, was investigated by transient absorption spectroscopy in the ns-mu s time regime. Strong magnetic-field effects (MFE) were observed for two triads with a phenylene bridge between iridium complex sensitizer and NDI acceptor. For these triads, the lifetimes of the CS states increased from 0.6 mu s at zero field to 40 mu s at about 2 T. Substituting the phenylene by a biphenyl bridge causes the lifetime of the CS state at zero field to increase by more than 2 orders of magnitude (tau = 79 mu s) and the MFE to disappear almost completely. The kinetic MFE was analyzed in the framework of a generalized Hayashi-Nagakura scheme describing coherent (5, T-0 <-> T-+/- as well as incoherent (S, T-0 reversible arrow T-+/-) processes by a single rate constant k(+/-). The magnetic-field dependence of k(+/-). of the triads with phenylene bridge spans 2 orders of magnitude and exhibits a biphasic behavior characterized by a superposition of two Lorentzians. This biphasic MFE is observed for the first time and is clearly attributable to the coherent (B < 10 mT) and incoherent (10 mT < B < 2 T) domains of spin motion induced by isotropic and anisotropic hyperfine coupling. The parameters of both domains are well understood in terms of the structural properties of the two triads, including the effect of electron hopping in the triad with two donor moieties. The kinetic model also accounts for the reduction of the MFE on reducing the rate constant of charge recombination in the triad with the biphenyl bridge.