Rahanyan Nelli, Duttwyler Simon, Linden Anthony, Baldridge Kim K, Siegel Jay S
Department of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland.
Dalton Trans. 2014 Jul 28;43(28):11027-38. doi: 10.1039/c4dt01460j.
Reactions of 7,10-disubstituted diazafluoranthene derivatives with three different silver(I) salts AgX (X = PF6, SbF6, CB11HCl11) and [Cu(CH3CN)4]PF6 afforded complexes exhibiting five different motifs. The crystal structures of the free ligands and nine new complexes from this series of reactions are reported. The use of 2,5-di-tert-butyl-7,10-di(pyridin-2-yl)-8,9-diazafluoranthene as a ligand leads to the formation of the tetranuclear compounds [Ag4(C32H30N4)4][PF6]4·3C6H6·4MeCN, [Ag4(C32H30N4)4][SbF6]4·4C5H12 and [Cu4(C32H30N4)4][PF6]4·8C3H6O, which exhibit "propeller" and saddle-type geometry, respectively, as well as a dinuclear complex [Ag2(C32H30N4)2][CHB11Cl11]2·4C6H4Cl2·CH2Cl2. The reactions involving the less sterically hindered 2,5-di-tert-butyl-7,10-di-(pyrimidin-2-yl)-8,9-diazafluoranthene and 2,5-di-tert-butyl-7,10-di(thiazol-2-yl)-8,9-diazafluoranthene afforded crystals of the dinuclear complexes [Ag2(C30H28N6)2][PF6]2·0.5CH2Cl2·0.5C6H5Cl·0.5C6H12, [Ag2(C30H28N6)2][SbF6]2·C3H6O·0.5C6H14·0.5C6H6, the polymeric species [Ag2(C28H26N4S2)2]n·2n[PF6]n·nC3H6O and the tetranuclear compounds [Cu4(C26H25N4S2)4][PF6]4·2CHCl3·2C3H6O and [Cu4(C30H28N6)4][PF6]4·2.17H2O, which possess saddle and grid-like architectures, respectively. Conformational analysis of the free ligands showed that they exhibit N-C-C-N torsion angles ranging from syn clinal (58°) to fully anti-periplanar conformations; the syn clinal conformation dominates in the complexes. The relative energies of the possible structural conformations of the synthesized ligands, as well as of oxazole disubstituted diazafluoranthenes, were calculated using density functional theory at the B97D/Def2-TZVPP level of theory.
7,10 - 二取代二氮杂荧蒽衍生物与三种不同的银（I）盐AgX（X = PF6、SbF6、CB11HCl11）以及[Cu(CH3CN)4]PF6反应，得到了呈现五种不同结构单元的配合物。报道了该系列反应中游离配体以及九个新配合物的晶体结构。使用2,5 - 二叔丁基 - 7,10 - 二（吡啶 - 2 - 基）- 8,9 - 二氮杂荧蒽作为配体，生成了四核化合物[Ag4(C32H30N4)4][PF6]4·3C6H6·4MeCN、[Ag4(C32H30N4)4][SbF6]4·4C5H12和[Cu4(C32H30N4)4][PF6]4·8C3H6O，它们分别呈现“螺旋桨”型和鞍型几何结构，还有双核配合物[Ag2(C32H30N4)2][CHB11Cl11]2·4C6H4Cl2·CH2Cl2。涉及空间位阻较小的2,5 - 二叔丁基 - 7,10 - 二（嘧啶 - 2 - 基）- 8,9 - 二氮杂荧蒽和2,5 - 二叔丁基 - 7,10 - 二（噻唑 - 2 - 基）- 8,9 - 二氮杂荧蒽的反应，得到了双核配合物[Ag2(C30H28N6)2][PF6]2·0.5CH2Cl2·0.5C6H5Cl·0.5C6H12、[Ag2(C30H28N6)2][SbF6]2·C3H6O·0.5C6H14·0.5C6H6的晶体，聚合物物种[Ag2(C28H26N4S2)2]n·2n[PF6]n·nC3H6O以及四核化合物[Cu4(C26H25N4S2)4][PF6]4·2CHCl3·2C3H6O和[Cu4(C30H28N6)4][PF6]4·2.17H2O，它们分别具有鞍型和网格状结构。游离配体的构象分析表明，它们的N - C - C - N扭转角范围从顺式斜交（58°）到完全反式共平面构象；顺式斜交构象在配合物中占主导。使用密度泛函理论在B97D/Def2 - TZVPP理论水平下计算了合成配体以及恶唑二取代二氮杂荧蒽可能的结构构象的相对能量。
