2-oxobenzo[d][1,3]dithiole-5-[1,3,5,7-tetramethyl-2,6-diethyl(4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)] | 1262393-08-7

• 英文名称: 2-oxobenzo[d][1,3]dithiole-5-[1,3,5,7-tetramethyl-2,6-diethyl(4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)]
• 英文别名: 2-oxobenzo[d][1,3]dithiole-5-(1,3,5,7-tetramethyl-2,6-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)
• CAS: 1262393-08-7
• 化学式: C₂₄H₂₅BF₂N₂OS₂
• 分子量: 470.415
• InChiKey: KJPAIDVBFCYOBH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 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：

  (2,2-联吡啶)二氯铂(II) 、 2-oxobenzo[d][1,3]dithiole-5-[1,3,5,7-tetramethyl-2,6-diethyl(4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)] 在 KOC(CH₃)3 作用下， 以 甲醇 为溶剂， 以34%的产率得到[Pt(S2C6H3C(C4N(CH3)2(CH2CH3))2)(2,2'-bipyridine)]
  参考文献：
  名称：

  Sensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy−Pt(II)(diimine)(dithiolate) Conjugates

  摘要：

  The dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV-vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based (1)pi pi* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based (MML)-M-1'CT (mixed metal-ligand to ligand charge transfer) excited state (tau(3)(SEnT) = 0.6 ps, tau(4)(SEnT) = 0.5 ps, and tau(6)(SEnT) = 1.6 ps), which undergoes rapid intersystem crossing to the (MMLL)-M-3'CT state due to the heavy Pt(II) ion. The (MMLL)-M-3'CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based 3 pi pi* excited state (tau(3)(TEnT) = 8.2 ps, tau(4)(TEnT) = 5 ps, and tau(6)(TEnT) = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.

  DOI：

  10.1021/ja1070366
• 作为产物：
  描述：

  2,4-二甲基-3-乙基吡咯 在 三氟化硼乙醚 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 132.0h， 生成 2-oxobenzo[d][1,3]dithiole-5-[1,3,5,7-tetramethyl-2,6-diethyl(4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)]
  参考文献：
  名称：

  Sensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy−Pt(II)(diimine)(dithiolate) Conjugates

  摘要：

  The dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV-vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based (1)pi pi* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based (MML)-M-1'CT (mixed metal-ligand to ligand charge transfer) excited state (tau(3)(SEnT) = 0.6 ps, tau(4)(SEnT) = 0.5 ps, and tau(6)(SEnT) = 1.6 ps), which undergoes rapid intersystem crossing to the (MMLL)-M-3'CT state due to the heavy Pt(II) ion. The (MMLL)-M-3'CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based 3 pi pi* excited state (tau(3)(TEnT) = 8.2 ps, tau(4)(TEnT) = 5 ps, and tau(6)(TEnT) = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.

  DOI：

  10.1021/ja1070366

文献信息

• Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes
  作者：Bo Zheng、Randy P. Sabatini、Wen-Fu Fu、Min-Sik Eum、William W. Brennessel、Lidong Wang、David W. McCamant、Richard Eisenberg

  DOI：10.1073/pnas.1509310112

  日期：2015.7.28

  The light-driven generation of H ₂ , the reductive side of water splitting, requires a light absorber or photosensitizer (PS) for electron-hole creation and photoinduced electron transfer. To increase the effectiveness of charge transfer chromophores as PSs, this report describes the attachment of a strongly absorbing organic dye (dipyrromethene-BF ₂ , commonly known as Bodipy) to Pt diimine dithiolate charge transfer chromophores and examination of systems containing these dyads for the light-driven generation of H ₂ . The use of these dyads increases system activity under green light irradiation (530 nm) relative to systems with either chromophore alone, validating such an approach in designing artificial photosynthetic systems. One dyad system exhibits both high activity and substantial durability (40,000 turnovers relative to PSs over 12 d).

  标题: 重要性 光驱动的H2生成，即水分裂的还原端，需要光吸收剂或光敏剂（PS）来产生电子-空穴并进行光诱导电子转移。为了增加电荷转移色素作为光敏剂的有效性，本报告描述了将强吸收的有机染料（二吡咯甲烷-BF2，通常称为Bodipy）附着到Pt二亚甲基二硫酸盐电荷转移色素上，并检查包含这些二聚体的系统对光驱动的H2生成的影响。使用这些二聚体在绿光照射（530 nm）下增加了系统活性，相对于仅有色素的系统，验证了这种设计人工光合系统的方法。其中一种二聚体系统表现出高活性和相当的耐久性（相对于PS在12天内的40,000次循环）。