4',5'-diaza-9'-(4,5-bis(methylthio)-1,3-dithiole-2-ylidene)-fluorene | 184360-21-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4',5'-diaza-9'-(4,5-bis(methylthio)-1,3-dithiole-2-ylidene)-fluorene
• 英文别名: 4,5-diaza-9-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]fluorene；4',5'-diaza-9'-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]fluorene；9'-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-4',5'-diazafluorene；4',5'-diaza-9'-(4,5-bis(methylthio)-1,3-thiol-2-ylidene)fluorene；4',5'-diaza-9'-(4,5-dimethylthio-1,3-dithiole-2-ylidene)fluorene；9'-(4,5-dimethylthio-1,3-dithiol-2-ylidene)-4',5'-diazafluorene；8-[4,5-Bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-3,13-diazatricyclo[7.4.0.02,7]trideca-1(9),2(7),3,5,10,12-hexaene
• CAS: 184360-21-2
• 化学式: C₁₆H₁₂N₂S₄
• 分子量: 360.549
• InChiKey: XLWNZGQLZJCYFH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  127
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4',5'-diaza-9'-(4,5-bis(methylthio)-1,3-dithiole-2-ylidene)-fluorene 在 methanate sodium 作用下， 以 甲醇 、 氯仿 为溶剂， 生成 (dmit)(4',5'-diaza-9'-(4,5-bis(methylthio)-1,3-dithiole-2-ylidene)-fluorene)palladium(II)
  参考文献：
  名称：

  ‘Unsymmetric’ palladium(II) complexes with ligand 4′,5′-diaza-9′-(4,5-disubstituted-1,3-dithiole-2-ylidene)-fluorene

  摘要：

  Four 'unsyminetric' complexes of palladium(II), [Pd(L)Cl-2] and [Pd(L)(dmit)], have been synthesized and characterized [L = 4', 5'-diaza-9'-(4.5-bis(methylthio)-1,3-dithiole-2-ylidene)-fluorene (L-1) and 4',5'-diaza-9'-(4,5-ethylenedithio-1,3-dithiole-2-ylidene)-fluorene (L-2)]. Single crystal Structure of [Pd(L-1)Cl-2] was determined, in which, the atoms of the molecule, except two methyl-groups, are conjugated in a quasi-plane. The planar molecules are further stacked forming two unequivalent columns with C...C, S...C and S...Cl contacts. The differences between dichloro complexes and dmit complexes in IR, UV and oxidation properties were discussed in detail. The dmit complexes exhibit LLCT hand from dmit (donor) to pi* of L-1 (acceptor). (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00176-2
• 作为产物：
  描述：

  4,5-双(甲硫代)-1,3-二硫杂环戊烯-2-硫酮 、 4,5-二氮芴-9-酮 在 三丁基,三丁酯 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以47%的产率得到4',5'-diaza-9'-(4,5-bis(methylthio)-1,3-dithiole-2-ylidene)-fluorene
  参考文献：
  名称：

  具有 4',5'-二氮杂-9'-(4,5-二取代-1,3-二硫醇-2-亚基)芴配体的金属配合物的合成、晶体结构和光学性质

  摘要：

  四种与 4',5'-二氮杂-9'-[4,5-双(甲硫基)-1,3-二硫醇-2-亚基]芴 (L1) 或 4',5'-二氮杂-9'-的复合物[4,5-双(乙硫基)-1,3-二硫醇-2-亚基]芴(L2)被合成。配合物[Co(L1)2Cl2]·2CH3OH(1)、[Cu(L2)2Cl2]·CH3OH·0.5CH2Cl2(3)和[Cu(L2)2Br2]·CH3OH(4)采用反式构型，化合物[Cd(L1)2(NO3)2](2)是顺式结构。发现短 S…S、C…C 和 C…S 触点在分子堆积中很重要。当形成金属配合物时，溶液和固态电子光谱都显示出分子内 CT 带的红移。固态中的这种分子内电荷跃迁相对于溶液中的跃迁增强。研究了化合物 1-4 的三阶非线性光学性质，结果表明，这些配合物呈现负 γ 值（约 10-30）并且是自散焦样品。这些 γ 值与已知的簇化合物相当。两个配体与金属中心的反式配位将有利于 NLO

  DOI：

  10.1002/ejic.200700862

文献信息

• Manganese( <scp>II</scp> ) Complexes Coordinated by a New Derivative of Bipyridine: 9′‐[4,5‐Bis(methylthio)‐1,3‐dithiol‐2‐ylidene]‐4′,5′‐diazafluorene
  作者：Qin‐Yu Zhu、Jie Dai、Ding‐Xian Jia、Li‐Hui Cao、Hai‐Hong Lin

  DOI：10.1002/ejic.200400330

  日期：2004.12

  Manganese(II) complexes with the ligand 9′-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-4′,5′-diazafluorene (L) have been synthesized, and the single-crystal structures of complexes [Mn(L)2(H2O)2](ClO4)2·(L)2·2C2H5OH·2CH3CN (1), [Mn(L)2Cl2]·1.5CH2Cl2 (2) and [Mn(L)2(NO3)2] (3) have been characterized. Complex 1 is trans-coordinated with N···H−O and S···S contacts, while the other two complexes are cis-coordinated

  锰 (II) 与配体 9'-[4,5-双(甲硫基)-1,3-二硫醇-2-亚基]-4',5'-二氮杂芴 (L) 已合成，单-配合物 [Mn(L)2(H2O)2](ClO4)2·(L)2·2C2H5OH·2CH3CN (1), [Mn(L)2Cl2]·1.5CH2Cl2 (2) 和 [Mn(L) )2(NO3)2] (3) 已被表征。配合物 1 与 N···H−O 和 S···S 接触是反式配位的，而另外两个配合物是顺式配位的，具有短的 π···π 堆积。还获得了无溶剂粉末样品，这些配合物在添加咪唑的情况下对 2 的分解表现出催化活性；高氯酸盐化合物是最有效的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• A Well Characterized Example of Conversion of Molecular Configuration Depending on the Existence of Intermolecular Interactions
  作者：Qin-Yu Zhu、Yong Zhang、Jie Dai、Guo-Qing Bian、Ding-Xian Jia、Jia-Sheng Zhang、Lin Guo

  DOI：10.1246/cl.2003.762

  日期：2003.8

  A new complex [Ag(L)2]ClO4·2CH2Cl2 (1) (L = 4′, 5′-diaza-9′-(4,5-dimethylthio-1,3-dithiole-2-ylidene)fluorene) was synthesized. It was confirmed by 1H NMR and X-ray structure determination that when the molecules crystallize out from solution, a conversion of molecular configuration occurs because of the strong intermolecular interactions.

  合成了一种新的复合物[Ag(L)2]ClO4-2CH2Cl2 (1)（L = 4′,5′-二氮杂-9′-(4,5-二甲基硫-1,3-二硫代-2-亚基)芴）。通过 1H NMR 和 X 射线结构测定证实，当分子从溶液中结晶出来时，由于分子间的强烈相互作用，分子构型发生了转换。
• π⋯π Interaction assembled silver(I) complexes with the ligand 4′,5′-diaza-9′-(4,5-disubstituted-1,3-dithiol-2-ylidene)fluorene
  作者：Qin-Yu Zhu、Jie Dai、Ding-Xian Jia、Li-Hui Cao、Hai-Hong Lin

  DOI：10.1016/j.poly.2004.07.007

  日期：2004.9

  Six silver(I) complexes with a new type of ligand, 4',5'-diaza-9'-(4,5-disubstituted-1,3-dithiol-2-ylidene)fluorene (L-n, n = 1, Me; 2, Et; 3, Bu substituted) have been obtained. Two of the complexes [Ag(L-1)(2)]ClO4 (1) and [Ag(L-1)(2)]SO3CF3 (4) have been structurally characterized by single-crystal X-ray diffraction. All of the Ag(I) ions are coordinated linearly by two ligands and the cations take planar structures. These planes are further assembled into one dimensional columns by Ag-Ag weak bonds, pi-pi stacking and (AgN)-N-... interactions. The UV-Vis and fluorescence spectra of the complexes were studied and the ligand-centered energy levels are not changed dramatically when the complexes are formed. (C) 2004 Elsevier Ltd. All rights reserved.
• SYNTHESIS AND CHARACTERIZATION OF COPPER(I) COMPLEXES WITH 4′,5′-DIAZA-9′-(4,5-DIAZA-9′-(4,5-DISUBSTITUTED-1,3-DITHIOL-2-YLIDENE)FLOURENES
  作者：Qin-Yu Zhu、Jie Dai、Guo-Qing Bian、Xin Wang、Wei Yang、Ze-Min Yan

  DOI：10.1081/sim-120005617

  日期：2002.11.7

  Two sets of copper(I) halide complexes with the new type of ligands,4',5'-diaza-9'-(4,5-ethylenethio 1,3-dithiole-2-ylidene)-fluorene (L-1) and 4,5-diaza-9-(4,5-dimethylthio-1,3-dithiole2-ylidene)fluorene (L-2), were prepared, [Cu(L-1)X] (X=Cl, Br, I) and [Cu(L-2)(n)X] (X = Cl, Br, n = 1; X = I; n = 0.5). The insoluble coordination polymers were characterized on the basis of the data obtained from elemental analyses, atomic absorption, IR, UV-Visible and fluorescence spectra. The conductivity of the iodine-doped complexes was also studied at room temperature (10(-6)-10(-8) S cm(-1)). Ligand-centered oxidation is considered to be the reason of the conductivity.
• Synthesis, crystal structures, and characterization of 4,5-diaza-9-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-fluorene (L) metal complexes [(TPyA)MII(L)](SbF6)2 (MII=Mn, Fe, Co; TPyA=tris(2-pyridylmethyl)amine)
  作者：Tanner Culpitt、Ilia A. Guzei、Lara C. Spencer、Andrew Simonson、Joel S. Miller、Megan R. Wimmer、Kendric J. Nelson

  DOI：10.1016/j.ica.2014.12.004

  日期：2015.3

  Transition metal complexes incorporating 9'-(4,5-dimethyl-1,3-dithiol-2-ylidene)-4',5'-diazafluorene (L) have been synthesized and single crystal structures of [(TPyA)Mn-II(L)](SbF6)(2) (1), [(TPyA)Fe-II(L)](SbF6)(2) (2), and [(TPyA)Co-II(L)](SbF6)(2) (3) (where TPyA = tris(2-pyridylmethyl) amine) have been characterized. In addition, spectroscopic analysis (IR and UV-Vis) and temperature dependent magnetic susceptibility measurements are reported for all new complexes. Compounds 1-3 are isostructural. Solid-state IR and solution UV-Vis spectra in dichloromethane (CH2Cl2) are consistent with other metal complexes with the ligand L bound to the metal. However, when complexes 1-3 are dissolved in acetone and acetonitrile the ligand L is labile enough to result in a complex with C3H6O or MeCN in the coordination sphere, respectively. This suggests L is more substitutionally labile than C3H6O and MeCN. Magnetic analyses of 1-3 revealed weak ferromagnetic interactions for 1 and 3 and weak antiferromagnetic interactions for 2. These new molecular synthons may have further applications in the synthesis of new heterobimetallic dinuclear complexes by removal of the methyl group from the dithiolate-end of the ligand L that is unbound to a metal ion at this point. Published by Elsevier B.V.