5,9,14,18,23,27,32,36-八丁氧基-2,3-萘酞菁镍(II) | 155773-70-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 中文名称: 5,9,14,18,23,27,32,36-八丁氧基-2,3-萘酞菁镍(II)
• 中文别名: 5,9,14,18,23,27,32,36-八丁氧基-2,3-萘酞菁镍(II)盐
• 英文名称: Ni(II) octabutoxynaphthalocyanine
• 英文别名: Ni(5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine)；Ni(5,9,14,18,23,27,32,36-octabutoxynaphthalocyanine(2-))；nickel(2+);5,12,18,25,31,38,44,51-octabutoxy-2,15,28,41,53,55-hexaza-54,56-diazanidatridecacyclo[40.10.1.13,14.116,27.129,40.04,13.06,11.017,26.019,24.030,39.032,37.043,52.045,50]hexapentaconta-1,3,5,7,9,11,13,15,17,19,21,23,25,27(55),28,30,32,34,36,38,40,42(53),43,45,47,49,51-heptacosaene
• CAS: 155773-70-9
• 化学式: C₈₀H₈₈N₈NiO₈
• 分子量: 1348.32
• InChiKey: ZRFVVSDVYUSJMJ-UHFFFAOYSA-N

物化性质

• 熔点：
  >300 °C (lit.)
• 稳定性/保质期：
  在常温常压下保持稳定，应避免与强氧化剂接触。

计算性质

• 辛醇/水分配系数(LogP)：
  20.17
• 重原子数：
  97
• 可旋转键数：
  32
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  150
• 氢给体数：
  0
• 氢受体数：
  12

安全信息

• 危险品标志：
  T
• 安全说明：
  S36/37/39,S45,S53
• 危险类别码：
  R49,R43
• WGK Germany：
  3

反应信息

• 作为产物：
  描述：

  5,9,14,18,23,27,32,36-八丁氧基-2,3-萘甲醛花菁 、 nickel(II) acetate tetrahydrate 在 1,8-diazabicyclo[5.4.0]undec-7-ene 作用下， 以 正丁醇 为溶剂， 以63%的产率得到5,9,14,18,23,27,32,36-八丁氧基-2,3-萘酞菁镍(II)
  参考文献：
  名称：

  Effects of Benzoannulation and α-Octabutoxy Substitution on the Photophysical Behavior of Nickel Phthalocyanines:  A Combined Experimental and DFT/TDDFT Study

  摘要：

  The photophysical properties of a group of Ni(II)-centered tetrapyrroles have been investigated by ultrafast transient absorption spectrometry and DFT/TDDFT methods in order to characterize the impacts of alpha-octabutoxy substitution and benzoannulation on the deactivation pathways of the S-1(pi,pi*) state. The compounds examined were NiPc, NiNc, NiPc(OBu)(8), and NiNc(OBu)(8), where Pc = phthalocyanine and Nc = naphthalocyanine. It was found that the S-1(pi,pi*) state of NiNc(OBu)(8) deactivated within the time resolution of the instrument (200 fs) to a vibrationally hot T-1(pi,pi*) state. The quasidegeneracy of the S-1(pi,pi*) and (3)(d(z2),d(x2-y2)) states allowed for fast intersystem crossing (ISC) to occur. After vibrational relaxation (ca. 2.5 ps), the T-1(pi,pi*) converted rapidly (ca. 19 ps lifetime) and reversibly into the (LMCT)-L-3(pi,d(x2-y2)) state. The equilibrium state, so generated, decayed to the ground state with a lifetime of ca. 500 ps. Peripheral substitution of the Pc ring significantly modified the photodeactivation mechanism of the S-1(pi,pi*) by inducing substantial changes in the relative energies of the S-1(pi,pi*), (3)(d(pi),d(x2-y2)), (3)(d(z2,),d(x2-y2)), T-1(pi,pi*), and (LMCT)-L-1,3(pi,d(x2-y2)) excited states. The location of the Gouterman LUMOs and the unoccupied metal level (d(x2-y2)) with respect to the HOMO is crucial for the actual position of these states. In NiPc, the S-1(pi,pi*) state underwent ultrafast (200 fs) ISC into a hot (d,d) state. Vibrational cooling (ca. 20 ps lifetime) resulted in a cold (d(z2),d(x2-y2)) state, which repopulated the ground state with a 300 ps lifetime. In NiPc(OBu)(8), the S-1(pi,pi*) state deactivated through the (3)(d(z2),d(x2)>(-y2)), which in turn converted to the (LMCT)-L-3(pi,d(x2-y2)) state, which finally repopulated the ground state with a lifetime of 640 ps. Insufficient solubility of NiNc in noncoordinating solvents prevented transient absorption data from being obtained for this compound. However, the TDDFT calculations were used to make speculations about the photoproperties.

  DOI：

  10.1021/ic061524o

文献信息

• Effects of Benzoannulation and α-Octabutoxy Substitution on the Photophysical Behavior of Nickel Phthalocyanines:  A Combined Experimental and DFT/TDDFT Study
  作者：Alexandra V. Soldatova、Junhwan Kim、Xinzhang Peng、Angela Rosa、Giampaolo Ricciardi、Malcolm E. Kenney、Michael A. J. Rodgers

  DOI：10.1021/ic061524o

  日期：2007.3.1

  The photophysical properties of a group of Ni(II)-centered tetrapyrroles have been investigated by ultrafast transient absorption spectrometry and DFT/TDDFT methods in order to characterize the impacts of alpha-octabutoxy substitution and benzoannulation on the deactivation pathways of the S-1(pi,pi*) state. The compounds examined were NiPc, NiNc, NiPc(OBu)(8), and NiNc(OBu)(8), where Pc = phthalocyanine and Nc = naphthalocyanine. It was found that the S-1(pi,pi*) state of NiNc(OBu)(8) deactivated within the time resolution of the instrument (200 fs) to a vibrationally hot T-1(pi,pi*) state. The quasidegeneracy of the S-1(pi,pi*) and (3)(d(z2),d(x2-y2)) states allowed for fast intersystem crossing (ISC) to occur. After vibrational relaxation (ca. 2.5 ps), the T-1(pi,pi*) converted rapidly (ca. 19 ps lifetime) and reversibly into the (LMCT)-L-3(pi,d(x2-y2)) state. The equilibrium state, so generated, decayed to the ground state with a lifetime of ca. 500 ps. Peripheral substitution of the Pc ring significantly modified the photodeactivation mechanism of the S-1(pi,pi*) by inducing substantial changes in the relative energies of the S-1(pi,pi*), (3)(d(pi),d(x2-y2)), (3)(d(z2,),d(x2-y2)), T-1(pi,pi*), and (LMCT)-L-1,3(pi,d(x2-y2)) excited states. The location of the Gouterman LUMOs and the unoccupied metal level (d(x2-y2)) with respect to the HOMO is crucial for the actual position of these states. In NiPc, the S-1(pi,pi*) state underwent ultrafast (200 fs) ISC into a hot (d,d) state. Vibrational cooling (ca. 20 ps lifetime) resulted in a cold (d(z2),d(x2-y2)) state, which repopulated the ground state with a 300 ps lifetime. In NiPc(OBu)(8), the S-1(pi,pi*) state deactivated through the (3)(d(z2),d(x2)>(-y2)), which in turn converted to the (LMCT)-L-3(pi,d(x2-y2)) state, which finally repopulated the ground state with a lifetime of 640 ps. Insufficient solubility of NiNc in noncoordinating solvents prevented transient absorption data from being obtained for this compound. However, the TDDFT calculations were used to make speculations about the photoproperties.