dichloro(bis(mesityl)biazanaphthenequinone)platinum(II) | 910650-64-5

• 英文名称: dichloro(bis(mesityl)biazanaphthenequinone)platinum(II)
• 英文别名: [Pt(mesBIAN)]Cl2；[PtCl2(bis(mesitylimino)acenaphthene)]；Pt(bis(mesitylimino)acenaphthene)Cl2；PtCl2(bis(mesitylimino)acenaphthene)；PtCl2(MesBIAN)
• CAS: 910650-64-5
• 化学式: C₃₀H₂₈Cl₂N₂Pt
• 分子量: 682.552
• InChiKey: IZYRZRGIRPXTAF-NFSZIFMVSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  dichloro(bis(mesityl)biazanaphthenequinone)platinum(II) 在 cobaltocene 作用下， 生成 [PtCl2(bis(mesitylimino)acenaphthene)](1-)
  参考文献：
  名称：

  Near-Infrared Luminescence from Platinum(II) Diimine Compounds

  摘要：

  Square-planar Pt( II) complexes of the bis( mesitylimino) acenaphthene ( mesBIAN) ligand are emissive from a MMLL'CT excited state in a dichloromethane solution at room temperature. Investigation of the nature of the frontier orbitals in these near-IR emitters by a combination of emission spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations suggests that emission is enabled by the presence of low-lying ligand pi* orbitals on the mesBIAN.

  DOI：

  10.1021/ic060399d
• 作为产物：
  描述：

  bis[N-(2,4,6-trimethylphenyl)imino]acenaphthene 、 potassium trichloro(ethylene)platinate(II) 生成 dichloro(bis(mesityl)biazanaphthenequinone)platinum(II)
  参考文献：
  名称：

  Near-Infrared Luminescence from Platinum(II) Diimine Compounds

  摘要：

  Square-planar Pt( II) complexes of the bis( mesitylimino) acenaphthene ( mesBIAN) ligand are emissive from a MMLL'CT excited state in a dichloromethane solution at room temperature. Investigation of the nature of the frontier orbitals in these near-IR emitters by a combination of emission spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations suggests that emission is enabled by the presence of low-lying ligand pi* orbitals on the mesBIAN.

  DOI：

  10.1021/ic060399d

文献信息

• Photophysical Properties of Platinum(II)−Acetylide Complexes: the Effect of a Strongly Electron-Accepting Diimine Ligand on Excited-State Structure
  作者：Christopher J. Adams、Natalie Fey、Zoë A. Harrison、Igor V. Sazanovich、Michael Towrie、Julia A. Weinstein

  DOI：10.1021/ic800850h

  日期：2008.9.15

  copper(I) chloride, in which the copper atom is bonded to the two acetylide triple bonds. 1-5 each undergo an irreversible oxidation, and a reversible one-electron reduction to generate a stable anion. ESR studies of 1(-)-5(-) show that the unpaired electron is localized mainly on the pi* orbital of the coordinated MesBIAN ligand, with about 10% platinum contribution to the singly occupied molecular orbital

  化合物[Pt（MesBIAN）（C [三键] CR）2]（R = C6H4-CN-p，1; SiMe3，2; -CF3-p，3; C6H5，4; -CH3-p 5 ）MesBIAN = bis（mesitylimino）acenaphthene}已合成；报告了4和5的X射线晶体结构测定以及起始原料[Pt（MesBIAN）Cl2]。用二碘化学氧化4会生成中间的铂（IV）双（乙炔）二碘铂络合物，然后将其偶联并还原为乙炔，成为乙炔配体，从而导致[Pt（MesBIAN）I2] 6的生成。化合物2容易与氯化铜（I）形成加合物2a，其中铜原子键合至两个乙炔三键。1-5各自经历不可逆的氧化和可逆的单电子还原以产生稳定的阴离子。1（-）-5（-）的ESR研究表明，未配对的电子主要位于配位MesBIAN配体的pi *轨道上，其中约10％的铂对单占据的分子轨道（SOMO）起作用。该化合物在紫外/可见光谱中约500
• [Pt(mesBIAN)(tda)]: A near-infrared emitter and singlet oxygen sensitizer
  作者：Aaron A. Rachford、Fei Hua、Christopher J. Adams、Felix N. Castellano

  DOI：10.1039/b818177b

  日期：——

  The synthesis and subsequent photophysical investigation of [Pt(mesBIAN)(tda)], where mesBIAN is bis(mesitylimino)acenaphthene and tda is tolan-2,2′-diacetylide, reveal excited-state characteristics best described as triplet charge transfer (3CT) in nature upon visible light excitation. Large ground-state dipole moments are apparent as the absorption spectrum dramatically red-shifts with decreasing solvent polarity. The 3CT excited state is significantly lower in energy than the ligand-centered 3tda excited-state, as confirmed by steady-state and time-resolved techniques. Singlet oxygen sensitization studies demonstrate that 1O2 production occurs by diffusive quenching from the photo-excited 3CT state (ΦΔ = 0.24, λmax∼1270 nm) in oxygen-saturated dichloromethane.

  Pt(mesBIAN)(tda)的合成及随后的光物理研究揭示了在可见光激发下的激发态特征，其性质最适合描述为三重电荷转移（3CT）。随着溶剂极性的降低，吸收光谱会发生显著的红移，由此可见基态偶极矩很大。稳态和时间分辨技术证实，3CT 激发态的能量明显低于以配体为中心的 3tda 激发态。单线态氧敏化研究表明，在氧气饱和的二氯甲烷中，1O2 是通过光激发 3CT 态（ΦΔ = 0.24，λmax∼1270 nm）的扩散淬灭产生的。
• Ranking Solvent Interactions and Dielectric Constants with [Pt(mesBIAN)(tda)]: A Cautionary Tale for Polarity Determinations in Ionic Liquids
  作者：Gary A. Baker、Aaron A. Rachford、Felix N. Castellano、Sheila N. Baker

  DOI：10.1002/cphc.201200981

  日期：2013.4.2

  properties of [Pt(mesBIAN)(tda)] are studied in traditional molecular solvents and ionic liquids and duly compared along established empirical solvent parameter scales. The charge‐transfer absorption band of [Pt(mesBIAN)(tda)] is determined to be primarily dependent upon solvent acidity and dipolarity. Notably, ionic liquids do not obey the same well‐behaved trend as molecular solvents, highlighting

  在传统的分子溶剂和离子液体中研究了[Pt（mesBIAN）（tda）]的溶剂变色性质，并根据建立的经验溶剂参数量表进行了适当比较。确定[Pt（mesBIAN）（tda）]的电荷转移吸收带主要取决于溶剂的酸度和双极性。值得注意的是，离子液体没有遵循与分子溶剂相同的良好趋势，这突出了离子液体固有的复杂性和域（纳米）偏析。
• Synthesis, structures and properties of a new series of platinum–diimine–dithiolate complexes
  作者：Christopher J. Adams、Natalie Fey、Matthew Parfitt、Simon J. A. Pope、Julia A. Weinstein

  DOI：10.1039/b709252k

  日期：——

  [Pt(mesBIAN)SS] have been synthesised mesBIAN = bis(mesityl)biazanaphthenequinone; SS = 1,2-dithiooxalate (dto) 1, maleonitriledithiolate (mnt) 2, 1,2-benzenedithiolate (bdt) 3, 3,4-toluenedithiolate (tdt) 4 and 1,3-dithia-2-thione-4,5-dithiolate (dmit) 5}, and the X-ray crystal structures of 3 and 5 determined. Cyclic voltammetry reveals that all the compounds form stable anions, and ESR spectroscopy

  新的方形铂金二亚胺已经合成了–二硫代甲酸酯化合物[Pt（mesBIAN）SS]（mesBIAN = bis（mesityl）biazanaphthenequinone; SS = 1,2- dithiooxalate（DTO）1，maleonitriledithiolate（MNT）2，1,2- benzenedithiolate（BDT）3，3,4- toluenedithiolate（TDT）4和1,3-二硫杂-2-硫酮-4， 5-二硫醇盐（dmit）5 }，并确定3和5的X射线晶体结构。循环伏安法 揭示所有化合物均形成稳定的阴离子，并且 ESR光谱 这些阴离子表明SOMO基于mesBIAN 配体; 化合物2–5在其化合物中也显示出可逆的氧化波简历。计算研究表明，金属和二硫醇盐结合而成的轨道的电荷转移过程配体基于mesBIANπ*的LUMO导致这些化合物在UV /可见光谱中观察到的低