1-(7-ethynyl-9,9-dioctyl-9H-fluoren-2-yl)ethynylbenzene | 1367842-57-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 1-(7-ethynyl-9,9-dioctyl-9H-fluoren-2-yl)ethynylbenzene
• 英文别名: 2-Ethynyl-9,9-dioctyl-7-(2-phenylethynyl)fluorene；2-ethynyl-9,9-dioctyl-7-(2-phenylethynyl)fluorene
• CAS: 1367842-57-6
• 化学式: C₃₉H₄₆
• 分子量: 514.794
• InChiKey: RFTNYOVZCDEVSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.3
• 重原子数：
  39
• 可旋转键数：
  17
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  9,9-二辛基-2,7-二溴代芴 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 、 三苯基膦 、 potassium hydroxide 作用下， 以 异丙醇 为溶剂， 反应 16.0h， 生成 1-(7-ethynyl-9,9-dioctyl-9H-fluoren-2-yl)ethynylbenzene
  参考文献：
  名称：

  Tuning the photophysical properties of N^N Pt(ii) bisacetylide complexes with fluorene moiety and its applications for triplet–triplet-annihilation based upconversion

  摘要：

  含氟苯的芳香烃乙炔配体被用于制备N^NPt(II)双乙炔配合物，其中氟苯上的芳香取代基为酚基（Pt-1）、萘基（Pt-2）、蒽基（Pt-3）、芘基（Pt-4）、4-二苯胺苯基（Pt-5）和9,9-二正辛基氟苯（Pt-6）（其中N^N配体为4,4' -二叔丁基-2,2' -联吡啶，dbbpy）。所有配合物在室温下均显示出磷光。通过稳态发射光谱、T1态的寿命、77K下的发射光谱、自旋密度分析和时间分辨瞬态吸收光谱法，将Pt-1、Pt-5和Pt-6的发射性T1激发态归类为金属-配体电荷转移态（3MLCT），而Pt-2、Pt-3和Pt-4的发射性T1激发态则被鉴定为配体内态（3IL）。Pt-3（τ = 66.7μs）和Pt-4（τ = 54.7μs）显示出异常长寿命的T1激发态，相较于模型配合物dbbpy Pt(II)双苯乙炔（τ = 1.25μs）。观察到Pt-3在780nm处有蒽的室温磷光。氟苯的关键作用是将配合物的吸收移至光谱的红端，同时不降低配合物T1态的能级。这种独特的光谱调谐效应以及Pt-4的长寿命T1激发态的优势，通过配合物在三重态-三重态湮灭（TTA）基础上的上转换作为三重态敏化剂的增强性能得以体现；观察到Pt-4作为敏化剂的上转换量子产率（ΦUC）高达22.4%。其他在此描述的配合物几乎没有上转换。Pt-4高上转换量子产率的原因在于其对可见光的强吸收和长寿命的T1激发态。基于Pt-4的结果，我们提出弱磷光或非磷光的过渡金属配合物可以用作TTA上转换的三重态敏化剂，相较于目前用于TTA上转换的磷光三重态敏化剂。我们的结果将有助于设计过渡金属配合物，以增强光吸收及其后的级联光物理过程，同时不降低T1激发态能级，这对这些配合物在各种光物理过程中的应用作为三重态敏化剂至关重要。

  DOI：

  10.1039/c2jm15678d

文献信息

• Fluorene as π-conjugation linker in N^N Pt(ii) bisacetylide complexes and their applications for triplet–triplet annihilation based upconversion
  作者：Huimin Guo、Qiuting Li、Lihua Ma、Jianzhang Zhao

  DOI：10.1039/c2jm32074f

  日期：——

  Fluorene-containing N^N Pt(II) bisacetylide complexes were prepared, in which the fluorene moieties were connected to the Pt(II) center via acetylide bonds (–CC–). Different aryl groups were attached to the fluorene moiety, such as phenylacetylide (Pt-4), naphthalimide-4-acetylide (Pt-1) and in Pt-2, the fluorene moiety was changed to carbozale moiety. We found that with the fluorene linker between the arylacetylide and the Pt(II) center, the absorption of complexes in the visible range were intensified. All the complexes show room temperature (RT) phosphorescence. Furthermore, Pt-1 shows much longer triplet excited state lifetime (τ = 138.1 μs) than the analogue Pt-3 (τ = 47.4 μs). For Pt-2, with changing the fluorene moiety to carbazole moiety, the T1 state lifetime becomes much shorter (τ = 23.0 μs). Thus the one-atom (N vs. C) difference is crucial for the photophysical properties. The triplet excited state of Pt-1 was proved to be the intraligand excited state (3IL) by nanosecond time-resolved transient absorption spectroscopy, spin density analysis and emission at 77 K. The complexes were used as triplet sensitizers for triplet–triplet annihilation (TTA) upconversion. Upconversion quantum yield (ΦUC) up to 24.3% was observed for Pt-1. Under the same conditions the model complex Pt-4 shows no upconversion. The overall upconversion efficiency (η) of the new complexes are improved compared to the model complexes, such as Pt-2, Pt-3 and Pt-4. The improved upconversion efficiency was attributed to either the prolonged T1 excited state lifetime or the intensified absorption in the visible range. Our study on the fluorene-containing N^N Pt(II) bisacetylide complexes will be useful for designing new phosphorescent Pt(II) complexes and for their applications.

  我们制备了含芴的 N^N Pt（II）双乙酰络合物，其中芴分子通过乙酰键（âCCâ）与 Pt（II）中心相连。芴基上连接了不同的芳基，如苯基乙酰化物（Pt-4）、萘二甲酰亚胺-4-乙酰化物（Pt-1），而在 Pt-2 中，芴基变成了羧基。我们发现，在芳基乙酰化物和铂(II)中心之间添加芴连接物后，配合物在可见光范围内的吸收增强。所有复合物都显示出室温磷光。此外，Pt-1 的三重激发态寿命（Ï = 138.1 δ¼s）比类似物 Pt-3 的三重激发态寿命（Ï = 47.4 δ¼s）长得多。对于 Pt-2，当芴基变为咔唑基时，T1 态寿命会变得更短（Ï = 23.0 δ¼s）。因此，一个原子（N 与 C）的差异对于光物理特性至关重要。通过纳秒时间分辨瞬态吸收光谱、自旋密度分析以及在 77 K 下的发射，证明了 Pt-1 的三重激发态是配体内激发态（3IL）。Pt-1 的上转换量子产率（δUC）高达 24.3%。在相同条件下，模型复合物 Pt-4 没有出现上转换现象。与 Pt-2、Pt-3 和 Pt-4 等模型配合物相比，新配合物的整体上转换效率（δ-）有所提高。上转换效率的提高可归因于 T1 激发态寿命的延长或可见光范围内吸收的增强。我们对含芴 N^N Pt（II）双乙酰络合物的研究将有助于设计新的磷光铂（II）络合物及其应用。
• Tuning the photophysical properties of N^N Pt(ii) bisacetylide complexes with fluorene moiety and its applications for triplet–triplet-annihilation based upconversion
  作者：Qiuting Li、Huimin Guo、Lihua Ma、Wanhua Wu、Yifan Liu、Jianzhang Zhao

  DOI：10.1039/c2jm15678d

  日期：——

  Fluorene-containing aryl acetylide ligands were used to prepare N^NPt(II) bisacetylide complexes, where aryl substituents on the fluorene are phenyl (Pt-1), naphthal (Pt-2), anthranyl (Pt-3), pyrenyl (Pt-4), 4-diphenylaminophenyl (Pt-5) and 9,9-di-n-octylfluorene (Pt-6) (where N^N ligand = 4,4′-di-tert-butyl-2,2′-bipyridine, dbbpy). All the complexes show room temperature (RT) phosphorescence. The emissive T1 excited states of Pt-1, Pt-5 and Pt-6 were assigned as metal-to-ligand-charge-transfer state (3MLCT), whereas for Pt-2, Pt-3 and Pt-4, the emissive T1 excited states were identified as the intraligand state (3IL), based on steady state emission spectra, the lifetime of the T1 state, emission spectra at 77 K, spin density analysis and the time-resolved transient absorption spectroscopy. Exceptionally long lived T1 excited state was observed for Pt-3 (τ = 66.7 μs) and Pt-4 (τ = 54.7 μs), compared to a model complex dbbpy Pt(II) Bisphenylacetylide (τ = 1.25 μs). RT phosphorescence of anthracene was observed at 780 nm with Pt-3. The critical role of the fluorene is to move the absorption of the complexes to the red-end of the spectra, but at the same time, without compromising the energy level of the T1 state of the complexes. The advantage of this unique spectral tuning effect and the long-lived T1 excited states of Pt-4 was demonstrated by the enhanced performance of the complexes as triplet sensitizers for triplet–triplet annihilation (TTA) based upconversion; an upconversion quantum yield (ΦUC) up to 22.4% was observed with Pt-4 as the sensitizer. Other complexes described herein show negligible upconversion. The high upconversion quantum yield of Pt-4 is attributed to its intense absorption of visible light and long-lived T1 excited state. Based on the result of Pt-4, we propose that weakly phosphorescent, or non-phosphorescent transition metal complexes can be used as triplet sensitizers for TTA upconversion, compared to the phosphorescent triplet sensitizers currently used for TTA upconversion. Our results will be useful for the design of transition metal complexes to enhance the light-absorption and thereafter the cascade photophysical processes, without decreasing the T1 excited state energy levels, which are important for the application of the complexes as triplet sensitizers in various photophysical processes.

  含氟苯的芳香烃乙炔配体被用于制备N^NPt(II)双乙炔配合物，其中氟苯上的芳香取代基为酚基（Pt-1）、萘基（Pt-2）、蒽基（Pt-3）、芘基（Pt-4）、4-二苯胺苯基（Pt-5）和9,9-二正辛基氟苯（Pt-6）（其中N^N配体为4,4' -二叔丁基-2,2' -联吡啶，dbbpy）。所有配合物在室温下均显示出磷光。通过稳态发射光谱、T1态的寿命、77K下的发射光谱、自旋密度分析和时间分辨瞬态吸收光谱法，将Pt-1、Pt-5和Pt-6的发射性T1激发态归类为金属-配体电荷转移态（3MLCT），而Pt-2、Pt-3和Pt-4的发射性T1激发态则被鉴定为配体内态（3IL）。Pt-3（τ = 66.7μs）和Pt-4（τ = 54.7μs）显示出异常长寿命的T1激发态，相较于模型配合物dbbpy Pt(II)双苯乙炔（τ = 1.25μs）。观察到Pt-3在780nm处有蒽的室温磷光。氟苯的关键作用是将配合物的吸收移至光谱的红端，同时不降低配合物T1态的能级。这种独特的光谱调谐效应以及Pt-4的长寿命T1激发态的优势，通过配合物在三重态-三重态湮灭（TTA）基础上的上转换作为三重态敏化剂的增强性能得以体现；观察到Pt-4作为敏化剂的上转换量子产率（ΦUC）高达22.4%。其他在此描述的配合物几乎没有上转换。Pt-4高上转换量子产率的原因在于其对可见光的强吸收和长寿命的T1激发态。基于Pt-4的结果，我们提出弱磷光或非磷光的过渡金属配合物可以用作TTA上转换的三重态敏化剂，相较于目前用于TTA上转换的磷光三重态敏化剂。我们的结果将有助于设计过渡金属配合物，以增强光吸收及其后的级联光物理过程，同时不降低T1激发态能级，这对这些配合物在各种光物理过程中的应用作为三重态敏化剂至关重要。