4,6-bis(4-t-butylphenyl)pyrimidine | 1309879-70-6

• 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: 4,6-bis(4-t-butylphenyl)pyrimidine
• 英文别名: 4,6-di(4-tert-butylphenyl)pyrimidine；4,6-Bis(4-tert-butylphenyl)pyrimidine；4,6-bis(4-tert-butylphenyl)pyrimidine
• CAS: 1309879-70-6
• 化学式: C₂₄H₂₈N₂
• 分子量: 344.5
• InChiKey: QAYMLDJFIFYKAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,6-bis(4-t-butylphenyl)pyrimidine 、 [Ir(3,5-bis(4-tert-butylpyridin-2-yl)-2,6-difluoropyridine)Cl(μ-Cl)]₂ 在 silver trifluoromethanesulfonate 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 8.0h， 以59%的产率得到[Ir(3,5-bis(4-tert-butylpyridin-2-yl)-2,6-difluoropyridine)Cl]₂(C₂₄H₂₆N₂)
  参考文献：
  名称：

  当两个比一个更好时：非立体异构双核铱（iii）配合物发出的明亮的磷光†

  摘要：

  已经制备了八种双核铱（III）配合物的新家族，其特征在于4，6-二芳基嘧啶L y为双-N-C-配位桥联配体。金属离子还通过基于1，3-二（2-吡啶基）苯的末端N，C，N-环金属化配体L X，以及通过单齿氯化物或氰化物来配位。化合物的通式为{Ir L X Z } 2 L y（Z＝ Cl或CN）。该家族包括具有三个不同的L X配体和五个不同的二芳基嘧啶L y的实例，其中四个是二苯基嘧啶，一个是二噻吩基嘧啶。必需的配体已经通过标准的交叉偶联方法合成。配合物的合成涉及两个步骤，其中L X H与IrCl 3 ·3H 2 O反应形成[Ir L X Cl（μ-Cl）] 2形式的双核配合物，然后用二芳基嘧啶L y H 2。至关重要的是，每个复合物仅以单一化合物形式形成：强反式金属化环的影响决定了配体的相对位置，而对称取代的三齿配体的使用消除了当双双齿单元通过桥连的配体连接时获得的Λ和Δ对映体的可能性。该族

  DOI：

  10.1039/c6dt00881j
• 作为产物：
  描述：

  4,6-二氯嘧啶 、 4-叔丁基苯硼酸 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 24.0h， 以67%的产率得到4,6-bis(4-t-butylphenyl)pyrimidine
  参考文献：
  名称：

  Highly Luminescent Mixed-Metal Pt(II)/Ir(III) Complexes: Bis-Cyclometalation of 4,6-Diphenylpyrimidine As a Versatile Route to Rigid Multimetallic Assemblies

  摘要：

  The proligand 4,6-di-(4-tert-butylphenyl)pyrimidine LH2 can undergo cycloplatination with K2PtCl4 at one of the two aryl rings to give, after treatment with sodium acetylacetonate, a mononuclear complex Pt(N boolean AND C-LH)(acac) (denoted Pt). If an excess of K2PtCl4 is used, a dinuclear complex of the form [Pt(acac)](2){mu-(N boolean AND C-L-N boolean AND C)} (Pt-2) is obtained instead, where the pyrimidine ring acts as a bridging unit. Alternatively, the mononuclear complex can undergo cyclometalation with a different metal ion. Thus, reaction of Pt with IrCl3 center dot 3H(2)O (2:1 ratio) leads, after treatment with sodium acetylacetonate, to an unprecedented mixed-metal complex of the form Ir{mu-(N boolean AND C-L-N boolean AND C)Pt(acac)}(2)(acac) (Pt2Ir). The mononuclear iridium complex Ir(N boolean AND C-LH)(2)(acac) (Ir) has also been prepared for comparison. The UV-visible absorption and photoluminesence properties of the four complexes and of the proligand have been investigated. The complexes are all highly luminescent, with quantum yields of around 0.5 in solution at room temperature. The introduction of the additional metal centers is found to lead to a substantial red-shift in absorption and emission, with lambda(max) in the order Pt < Pt-2 < In < Pt2Ir. The trend is interpreted with the aid of electrochemical data and density functional theory calculations, which suggest that the red-shift is due primarily to a progressive stabilization of the lowest unoccupied molecular orbital (LUMO). The radiative decay constant is also increased. This versatile design strategy may offer a new approach for tuning and optimizing the luminescence properties of d-block metal complexes for contemporary applications.

  DOI：

  10.1021/ic200706e

文献信息

• Rigidly linking cyclometallated Ir(<scp>iii</scp>) and Pt(<scp>ii</scp>) centres: an efficient approach to strongly absorbing and highly phosphorescent red emitters
  作者：Graeme Turnbull、J. A. Gareth Williams、Valery N. Kozhevnikov

  DOI：10.1039/c7cc00656j

  日期：——

  Appending a cyclometallated platinum unit onto each of the three ligands of the archetypal fac-Ir(ppy)₃ complex leads to a highly efficient red emitter with a short luminescence decay time.

  将一个环金属铂单元添加到原型fac-Ir(ppy)₃配合物的三个配体上，导致产生一种高效的红色发光体，具有短的发光衰减时间。
• METAL COMPLEX, POLYMER COMPOUND AND DEVICE CONTAINING THOSE
  申请人：Akino Nobuhiko

  公开号：US20100019669A1

  公开（公告）日：2010-01-28

  Disclosed is a metal complex represented by the following formula (1). In the formula, M represents a metal atom; R 1 -R 8 respectively represent a hydrogen atom, a halogen atom or a monovalent group; or alternatively R 3 and R 4 , or R 5 and R 6 may combine together to form a ring.

  公开的金属配合物如下式(1)所示。在此式中，M代表金属原子；R1-R8分别代表氢原子、卤素原子或一价基团；或R3和R4，或R5和R6可以结合在一起形成环。
• Trinuclear Cyclometalated Iridium(III) Complex Exhibiting Intense Phosphorescence of an Unprecedented Rate
  作者：Marsel Z. Shafikov、Andrey V. Zaytsev、Valery N. Kozhevnikov

  DOI：10.1021/acs.inorgchem.3c03810

  日期：2024.1.15

  Herein, we present two novel cyclometalated Ir(III) complexes of dinuclear and trinuclear design, Ir2(dppm)3(acac)2 and Ir3(dppm)4(acac)3, respectively, where dppm is 4,6-di(4-tert-butylphenyl)pyrimidine ligand and acac is acetylacetonate ligand. In both cases, rac-diastereomers were isolated during the synthesis. The materials show intense phosphorescence of outstanding rates (kr = ΦPL/τ) with corresponding

  在此，我们提出了两种新型环金属化 Ir(III) 配合物，分别为双核和三核设计， Ir 2 (dppm) 3 (acac) 2和Ir 3 (dppm) 4 (acac) 3 ，其中dppm为 4,6-di (4-叔丁基苯基)嘧啶配体， acac是乙酰丙酮配体。在这两种情况下，外消旋非对映异构体在合成过程中均被分离出来。这些材料表现出出色速率 ( k r = Φ PL /τ) 的强磷光，双核Ir 2 (dppm) 3 (acac) 2的相应辐射衰减时间仅为 τ r = 1/ k r = 0.36 μs，甚至更短 τ对于三核Ir 3 (dppm) 4 (acac) 3 ， r = 0.30 μs，在环境温度下对掺杂聚苯乙烯薄膜样品进行测量。在低温条件下测量，三个 T 1亚态（I、III 和 III）的辐射衰变时间和亚态能量间隔为 τ I = 11.8 μs、τ II = 7.1 μs、τ III
• When two are better than one: bright phosphorescence from non-stereogenic dinuclear iridium(<scp>iii</scp>) complexes
  作者：Ruth E. Daniels、Stacey Culham、Michael Hunter、Marcus C. Durrant、Michael R. Probert、William Clegg、J. A. Gareth Williams、Valery N. Kozhevnikov

  DOI：10.1039/c6dt00881j

  日期：——

  highest-energy emitter is the cyanide derivative whilst the lowest is the complex with the dithienylpyrimidine. The trends in both the absorption and emission energies as a function of ligand substituent have been rationalised accurately with the aid of TD-DFT calculations. The lowest-excited singlet and triplet levels correlate with the trend in the HOMO–LUMO gap. All the complexes have quantum yields that are

  已经制备了八种双核铱（III）配合物的新家族，其特征在于4，6-二芳基嘧啶L y为双-N-C-配位桥联配体。金属离子还通过基于1，3-二（2-吡啶基）苯的末端N，C，N-环金属化配体L X，以及通过单齿氯化物或氰化物来配位。化合物的通式为Ir L X Z } 2 L y（Z＝ Cl或CN）。该家族包括具有三个不同的L X配体和五个不同的二芳基嘧啶L y的实例，其中四个是二苯基嘧啶，一个是二噻吩基嘧啶。必需的配体已经通过标准的交叉偶联方法合成。配合物的合成涉及两个步骤，其中L X H与IrCl 3 ·3H 2 O反应形成[Ir L X Cl（μ-Cl）] 2形式的双核配合物，然后用二芳基嘧啶L y H 2。至关重要的是，每个复合物仅以单一化合物形式形成：强反式金属化环的影响决定了配体的相对位置，而对称取代的三齿配体的使用消除了当双双齿单元通过桥连的配体连接时获得的Λ和Δ对映体的可能性。该族
• Highly Luminescent Mixed-Metal Pt(II)/Ir(III) Complexes: Bis-Cyclometalation of 4,6-Diphenylpyrimidine As a Versatile Route to Rigid Multimetallic Assemblies
  作者：Valery N. Kozhevnikov、Marcus C. Durrant、J. A. Gareth Williams

  DOI：10.1021/ic200706e

  日期：2011.7.4

  The proligand 4,6-di-(4-tert-butylphenyl)pyrimidine LH2 can undergo cycloplatination with K2PtCl4 at one of the two aryl rings to give, after treatment with sodium acetylacetonate, a mononuclear complex Pt(N boolean AND C-LH)(acac) (denoted Pt). If an excess of K2PtCl4 is used, a dinuclear complex of the form [Pt(acac)](2)mu-(N boolean AND C-L-N boolean AND C)} (Pt-2) is obtained instead, where the pyrimidine ring acts as a bridging unit. Alternatively, the mononuclear complex can undergo cyclometalation with a different metal ion. Thus, reaction of Pt with IrCl3 center dot 3H(2)O (2:1 ratio) leads, after treatment with sodium acetylacetonate, to an unprecedented mixed-metal complex of the form Irmu-(N boolean AND C-L-N boolean AND C)Pt(acac)}(2)(acac) (Pt2Ir). The mononuclear iridium complex Ir(N boolean AND C-LH)(2)(acac) (Ir) has also been prepared for comparison. The UV-visible absorption and photoluminesence properties of the four complexes and of the proligand have been investigated. The complexes are all highly luminescent, with quantum yields of around 0.5 in solution at room temperature. The introduction of the additional metal centers is found to lead to a substantial red-shift in absorption and emission, with lambda(max) in the order Pt < Pt-2 < In < Pt2Ir. The trend is interpreted with the aid of electrochemical data and density functional theory calculations, which suggest that the red-shift is due primarily to a progressive stabilization of the lowest unoccupied molecular orbital (LUMO). The radiative decay constant is also increased. This versatile design strategy may offer a new approach for tuning and optimizing the luminescence properties of d-block metal complexes for contemporary applications.