Metal-organic frameworks (MOFs) can be prepared from oligomeric organic ligands to prepare materials referred to as oligoMOFs. Studies of oligoMOFs are relatively limited, with most existing reports focused on fundamental structure-property relationships. In this report, functional groups, such as terminal alkynes and pyridine groups, are installed on the tether between 1,4-benzene dicarboxylic acid (H2bdc) groups of the dimer ligands. It was found that the position of the pyridine donor atom had pronounced effects on the synthesis and structure of Zn(II)-based isoreticular MOFs (IRMOF-1 analog, oligoIRMOF). Importantly, simple H2bdc ligands with pendant pyridine groups (i.e., not part of an dimeric ligand), were unable to produce crystalline phases or produced new MOF phases, showing the importance of the oligomeric ligand in directing structure. Dimeric ligands with two H2bdc groups and a terminal alkyne produced a crystalline and porous oligoIRMOF that enables postsynthetic modification (PSM) via ‘click’ chemistry to introduce other functional groups into the pores of the material. This oligoIRMOF could be cross-linked using reagents containing multiple azide functional sites. Taken together, these studies are among the first examples of oligoMOFs with functionalized tethers and demonstrate the versatility, utility, and unique opportunities for new chemistry provided by oligoMOFs.

中文翻译：

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由具有功能化系绳的寡聚配体生成的金属有机框架


金属有机框架 （MOF） 可由低聚有机配体制备，以制备称为 oligoMOF 的材料。对 oligoMOF 的研究相对有限，大多数现有报告都集中在基本的结构-性质关系上。在本报告中，官能团（例如末端炔烃和吡啶基团）安装在二聚体配体的 1,4-苯二羧酸 （H2bdc） 基团之间的系绳上。研究发现，吡啶供体原子的位置对 Zn（II） 基等网状 MOFs（IRMOF-1 类似物，oligoIRMOF）的合成和结构有显著影响。重要的是，具有悬垂吡啶基团的简单 H2bdc 配体（即，不是二聚体配体的一部分）无法产生结晶相或产生新的 MOF 相，这表明寡聚配体在指导结构中的重要性。具有两个 H2bdc 基团和一个末端炔烃的二聚体配体产生结晶和多孔的 oligoIRMOF，它可以通过“点击”化学将其他官能团引入材料的孔隙中，从而实现合成后修饰 （PSM）。这种 oligoIRMOF 可以使用含有多个叠氮化物功能位点的试剂进行交联。综上所述，这些研究是具有功能化系绳的 oligoMOF 的首批例子之一，并证明了 oligoMOF 为新化学提供的多功能性、实用性和独特机会。