6,6'-diphenyl-4,4′-bipyrimidine | 866722-56-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 6,6'-diphenyl-4,4′-bipyrimidine
• 英文别名: 6,6'-diphenyl-4,4'-bipyrimidine；Ph2bpm；dpb；4-Phenyl-6-(6-phenylpyrimidin-4-yl)pyrimidine
• CAS: 866722-56-7
• 化学式: C₂₀H₁₄N₄
• 分子量: 310.358
• InChiKey: YYFULIDTHXTUNU-UHFFFAOYSA-N

物化性质

• 熔点：
  199-201 °C(Solv: methanol (67-56-1))
• 沸点：
  538.5±45.0 °C(Predicted)
• 密度：
  1.202±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6,6'-diphenyl-4,4′-bipyrimidine 、 五羰基溴化锰(I) 以 二氯甲烷 为溶剂， 以28%的产率得到
  参考文献：
  名称：

  第7组fac [[M（CO）3] +配合物（M = Mn，Re）的MLCT与联吡啶，吡啶基吡嗪，氮杂吡啶和吡啶-2-基甲亚胺型配体的相关性，以进行合理的photoCORM设计

  摘要：

  通过比较总共50个带有联吡啶的物种，获得了结构相关的fac- [M（CO）3 L 2 Br]配合物（M = Mn，Re; L 2 =双齿配体）的MLCT吸收最大值的数学相关性，吡啶基吡嗪，偶氮吡啶和吡啶-2-基甲胺L 2类型配体。经验关系首先通过对先前发布的26种复合物的MLCT吸收最大值进行初步比较得出，然后用于预测其他24种物种的相同吸收值。为了检查预测的有效性，准备了几种新的配合物。对它们进行了光谱表征，并在可能的情况下阐明了其X射线固态结构。初始的数学相关性可以预测未知物种的MLCT吸收最大值，平均差异为12 nm。随后利用以下导出的公式Calc Mn m LCT =（Obs Re MLCT /0.88）– 15.1将关系精炼为平均误差为6 nm。计算Mn m LCT = Mn配合物MLCT和Obs Re的预测值MLCT =实验观察到的Re配合物的MLCT转变。从长远来看，相关性和

  DOI：

  10.1002/ejic.201900568
• 作为产物：
  描述：

  3 - （二甲氨基）- 1 -苯基 -2-丙烯-1-酮 在 sodium ethanolate 、 sodium 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 53.0h， 生成 6,6'-diphenyl-4,4′-bipyrimidine
  参考文献：
  名称：

  通过自由基阴离子偶联合成一系列新型 6,6'-二取代 4,4'-双嘧啶：用于配位化学的新型 π 受体配体

  摘要：

  一个新的 6,6'-二取代 4,4'-联嘧啶配体家族已被制备和表征。通过循环伏安法测定的新配体的还原电位表明，这些新配体是比普遍存在的 2,2'-联吡啶配体更好的 π-受体，甚至优于未取代的母体 4,4'-联嘧啶配体。4,4'-联嘧啶的 6,6' 位置的取代基也会导致整个 UV 区域的 ππ* 和 nπ* 吸收发生红移。双嘧啶家族成员的 X 射线晶体结构表明，芳基取代基在固态时可以与嘧啶环共面。嘧啶环上的芳基取代基提供的额外电子离域作用有助于这些化合物更好的接受 π 能力。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  DOI：

  10.1002/ejoc.200500335

文献信息

• Spectroscopy and electrochemistry of new 6,6′-disubstituted-4,4′-bipyrimidine molybdenum(0) and tungsten(0) tetracarbonyl complexes
  作者：Elena Ioachim、Garry S Hanan

  DOI：10.1139/v05-127

  日期：2005.8.1

  new family of tetracarbonyl molybdenum(0) and tungsten(0) complexes based on new 6,6′-disubstituted-4,4′-bipyrimidine ligands was synthesized and characterized. The visible region of the absorption spectrum of each complex is dominated by a metal-to-ligand charge transfer band significantly lower in energy than the corresponding transition in 2,2′-bipyridine tetracarbonyl metal complexes. The 6,6′-substituents

  合成并表征了基于新的 6,6'-二取代-4,4'-联嘧啶配体的新系列四羰基钼 (0) 和钨 (0) 配合物。每个配合物的吸收光谱的可见区由金属到配体的电荷转移带支配，其能量显着低于 2,2'-联吡啶四羰基金属配合物的相应跃迁。6,6'-取代基在取代的双嘧啶中产生更大的 π-电子系统，因此是比母体 4,4'-双嘧啶更好的 π 受体。吸收带随着溶剂极性的降低而向红移。关键词：钼和钨，氮配体，四羰基金属配合物，吸收光谱，电化学。
• Novel Cu ^I Ethylene Complexes with 6,6′‐Diphenyl‐4,4′‐bipyrimidine Three‐Dimensionally Self‐Assembled by an Intermolecular π‐π Stacking Interaction and a C–H···N Contact
  作者：Masahiko Maekawa、Toshi Tominaga、Takashi Okubo、Takayoshi Kuroda‐Sowa、Megumu Munakata

  DOI：10.1002/ejic.200900533

  日期：2009.10

  packing structures are much different from the connection manners of an intermolecular π–π stacking interaction and a C–H···N contact, resulting in the self-assembly of CuI–C2H4 adducts with a unique three-dimensional network structure. The X-ray, 1H NMR, IR data support the assumption that the contribution of the larger CuIC2H4 π back-donation bonding is induced by the electron-releasing phenyl group

  四种新型 CuI–Ph2bpm/C2H4 加合物 [Cu(Ph2bpm)(C2H4)]X [X = BF4 (1a, 1b), ClO4 (2) 和 PF6 (3); 制备了 Ph2bpm = 6,6'-二苯基-4,4'-联嘧啶]，并通过 X 射线、1H NMR、IR 和 TG-DTA 分析对其进行了表征。CuI-Ph2bpm/C2H4 复合物 1a、1b、2 和 3 的分子结构基本相似：Cu 原子由 Ph2bpm 螯合位中的两个 N 原子配位，C2H4 的 C=C 键在三角平面几何结构中配位. 有趣的是，它们的晶体堆积结构与分子间π-π堆积相互作用和C-H…N接触的连接方式有很大不同，导致CuI-C2H4加合物的自组装具有独特的三维网络结构体。X 射线、1H 核磁共振、红外数据支持这样的假设，即较大的 CuIC2H4 π 回馈键的贡献是由释放电子的苯基引起的。(© Wiley-VCH Verlag
• Heteroleptic ruthenium(II) complexes based on 6,6′-disubstituted 4,4′-bipyrimidines: New room temperature red-emitting species
  作者：Elena Ioachim、Elaine A. Medlycott、Garry S. Hanan、Frédérique Loiseau、Vittorio Ricevuto、Sebastiano Campagna

  DOI：10.1016/j.inoche.2005.03.022

  日期：2005.6

  Abstract A new series of heteroleptic ruthenium(II) complexes based on 6,6′-disubstituted 4,4′-bipyrimidines (bpm) and two 2,2′-bipyridine (bpy) ligands have been prepared and their spectroscopic and electrochemical properties have been investigated. The complexes exhibit Ru-to-bpm metal-to-ligand charge transfer (MLCT) absorptions centered at about 540 nm and Ru-to-bpy MLCT absorptions centered at

  摘要 制备了一系列基于 6,6'-二取代 4,4'-联嘧啶 (bpm) 和两个 2,2'-联吡啶 (bpy) 配体的新型杂配钌 (II) 配合物，其光谱和电化学性质均优于被调查。该配合物表现出以约 540 nm 为中心的 Ru-to-bpm 金属-配体电荷转移 (MLCT) 吸收和以约 435 nm 为中心的 Ru-bpy MLCT 吸收。新的配合物在室温下在流体溶液中是发光的，它们是基于已知的三双齿单核 Ru(II) 配合物的最长波长发射器 (λmax > 780 nm) 之一。
• Synthesis and properties of Re(I) tricarbonyl complexes of 6,6′-disubstituted-4,4′-bipyrimidines with high energy excited states suitable for incorporation into polynuclear arrays
  作者：Elena Ioachim、Elaine A. Medlycott、Garry S. Hanan

  DOI：10.1016/j.ica.2005.09.042

  日期：2006.6

  A series of complexes [(N-N)Re(CO)(3)X](n) (N-N = 6,6'-diaryl-4,4-bipyrimidine, axial ligand X = Cl, MeCN, 4-phenyl-pyridine, or t-Bu-pyridine) have been synthesized and characterized. The substituent aryl on the bipyrimidine, as well as the axial ligand X, has important effects on the properties of these complexes. The co-planarity of the 4,4'-bipyrimidine core and its substituents contributes to the extent of pi-electron delocalization and, hence, to the redox and spectroscopic properties of the complexes. The complexes exhibit Re-to-bpm metal-to-ligand charge transfer absorptions in the range of 379-464 nm, which are red-shifted with the increase in the delocalization in the substituted bpm ligand and the increase in the donor character of the axial ligand. The electrochemical data support metal-based oxidations (from +1.07 to +1.40 V) and ligand-based reductions (from -0.62 to -0.75 V) and correlate well with those obtained by UV-Vis spectroscopy. The X-ray crystal structures of two of the complexes have also been investigated. (c) 2005 Elsevier B.V. All rights reserved.
• Synthesis and properties of red emitter Ru(II) complexes based on 6,6′-disubstituted-4,4′-bipyrimidine
  作者：Elena Ioachim、Elaine A. Medlycott、Garry S. Hanan、Frédérique Loiseau、Sebastiano Campagna

  DOI：10.1016/j.ica.2005.03.057

  日期：2006.2

  Heteroleptic complexes [Ru(bpy)(2)(R(2)bpm)](2+), where bpy = 2,2'-bipyridine and R(2)bpm = 6,6'-diaryl-4,4'-bipyrimidine, have been synthesized and characterized, together with the homoleptic complex [Ru(R(2)bPM)3](2+), in which R(2)bpm = 6,6'-diphenyl-4,4'-bipyrimidine. The substituent aryl on the bipyrimidine has significant effects on the properties of these complexes as compared to the parent [Ru(bpy)(2)(bpM)](2+) complex. The complexes exhibit Ru-to-bpm charge transfer (CT) absorptions centered at about 540 nm and Ru-to-bpy CT absorptions centered at about 435 nm. The assignment of the low energy absorptions is supported by the relative ease of the reduction of the new complexes as compared to [Ru(bpy)3](2+). The new complexes exhibit a relatively intense emission at room temperature, with lifetimes in the 10-50 ns range, with the homoleptic species exhibiting the higher-energy (maximum at 724 nm) and the longest-lived (tau = 48 ns) emission among the complexes. Luminescence lifetimes and quantum yields are governed by the energy gap law, indicating that direct deactivation to the ground state is the dominant relaxation pathway for 1-6, while thermally activated processes are inefficient. (c) 2005 Elsevier B.V. All rights reserved.