Marsden Jeremiah A, Haley Michael M
Department of Chemistry, Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA.
J Org Chem. 2005 Dec 9;70(25):10213-26. doi: 10.1021/jo050926v.
[structures: see text] The synthesis and optical properties of a series of multinanometer-sized substructures of the phenyl-diacetylene carbon allotrope, graphdiyne, are described. These molecules are among the largest and most complex annulenic systems yet prepared, with extension of linear conjugation in two-dimensions to over twice that of any previously reported planar macrocycle. The graphdiyne substructures are constructed through convergent syntheses, taking advantage of three key intermediates and silane-protected phenylacetylenes. Intramolecular macrocyclization of alpha,omega-polyyne precursors via Cu-mediated or Pd-catalyzed oxidative homocoupling affords five new graphdiyne "oligomers" possessing two to four fused 18-membered rings. The attempted synthesis of a six-ring analogue is also reported.
[结构：见正文] 描述了一系列苯基二乙炔碳同素异形体石墨二炔的多纳米尺寸子结构的合成及光学性质。这些分子是迄今制备的最大且最复杂的轮烯体系之一，其二维线性共轭的延伸长度超过此前报道的任何平面大环的两倍以上。石墨二炔子结构通过汇聚合成构建，利用了三种关键中间体和硅烷保护的苯乙炔。α,ω-聚炔前体通过铜介导或钯催化的氧化均偶联进行分子内大环化，得到了五个具有两到四个稠合18元环的新型石墨二炔“低聚物”。还报道了六环类似物的合成尝试。
