Synthesis and Single-Crystal X-ray Characterization of 4,4‘ ‘-Functionalized 4‘-(4-Bromophenyl)-2,2‘:6‘,2‘ ‘-terpyridines

To expand the utility of bis(terpyridine) metal connectivity, the selective symmetrical and unsymmetrical
4,4‘ ‘-functionalization (−CN, −Me, −CO2Me) of 4‘-(4-bromophenyl)-2,2‘:6‘,2‘ ‘-terpyridines was achieved
using the Kröhnke synthesis. The final substituted 2,2‘:6‘,2‘ ‘-terpyridines along with their corresponding
intermediates, 4a−c, were recrystallized and characterized by 1H NMR and 13C NMR as well as X-ray
crystallography; COSY correlations were also conducted to permit definitive proton assignment.

为拓展双(噻二氮杂茂)金属连接性的应用，通过克罗恩克合成法成功实现了对4'-（4-溴苯基）-2,2':6',2''-三噻二氮杂茂的4''位选择性对称及非对称功能化（-CN, -Me, -CO2Me）。最终得到的取代型2,2':6',2''-三噻二氮杂茂及其对应中间体4a-c，均经过重结晶处理，并通过1H NMR、13C NMR以及X射线晶体学进行了表征；此外，还进行了COSY相关性分析，以实现质子归属的明确确定。