| 170121-13-8

• CAS: 170121-13-8
• 化学式: Br*C₆H₁₃AuBrN₃P
• 分子量: 514.938
• InChiKey: WTFVWEARAKMEQQ-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  (1,3,5-triaza-7-phosphaadamantane)gold(I) bromide * MeCN 、 氢溴酸 以 氢溴酸 为溶剂， 生成
  参考文献：
  名称：

  Structures and Spectroscopic Properties of Gold(I) Complexes of 1,3,5-Triaza-7-phosphaadamantane (TPA). 2. Multiple-State Emission from (TPA)AuX (X = Cl, Br, I) Complexes

  摘要：

  Temperature-dependent photoluminescence (PL) and structural studies of (TPA)AuBr, 2, (TPA)AuI, 3, and [(TPAH)AuI][AuI2], 4, are reported. Unlike (TPA)AuCl, 1, compound 2 has two emission bands with relative intensities which depend upon the excitation wavelength used. Upon excitation at 320 nm, a strong orange emission centering at 647 nm is observed. Changing the excitation wavelength to 340 nm results in the observance of only a bright white, structured emission centering ca. 450 nm. Each of the two emission bands shows a distinct excitation spectrum, suggesting poor coupling between the excited states responsible for the emissions. Compared to that of 2, the LE band of 3 is blue-shifted to 617 nm, whereas the structured HE band is unshifted at ca. 450 nm. The relative intensity of the LE band to the HE band decreases (with no shift in energy) when the excitation wavelength is changed from 320 to 350 nm. Similar to those of 2, the emission bands of 3 also are sensitive to the excitation energy. The HE bands of both 2 and 3 are short lived (<10 ns) whereas the LE bands have lifetimes of 0.8 and 2.7 mu s, respectively. On the basis of these observations, the complexes appear to show multiple emitting states in their solid state structures. The systematic changes occurring with variation of the halide X and the lifetime data suggest that the LE band originates from a triplet metal-centered transition ((3)MC). The HE emission band appears to originate from a halide to metal charge transfer ((1)XMCT) excited state. Protonation of the ligand TPA significantly alters the PL properties of the complexes in accord with changes in the Au ... Au separation. The metal-centered LE band of the protonated complex (TPAHBr)AuBr, 2P, is observed at the blue-shifted position of 587 nm when compared to that of 2. Protonation of 3 with 0.1 N HCl produces 4. Compound 4 luminesces strongly with emission maxima at 655 nm at 78 K. A simple model that correlates the LE emission with the Au Au separation has been developed. The Au ... Au separations in these species are predicted from the position of the emission energy using the equation (E + P)/r = constant, where E is the emission energy, P is the singlet-tripler separation, and r corresponds to the Au ... Au distance. The result is supported by extended Huckel MO calculations where, upon shortening of the Au Au separation, the HOMO (sigma(u)) orbital destabilizes and causes a decrease in the HOMO-LUMO gap. Crystal data: [(TPAH)AuI][AuI2], 4, orthorhombic, Pnma (No. 62) with a = 15.453(3) Angstrom, b = 11.050(2) Angstrom, c = 9.113(2) Angstrom, V = 1556.1(5) Angstrom(3), Z = 4, R = 0.0419, R(W) = 0.0548.

  DOI：

  10.1021/ic00124a009