Moharana Sanjaya Kumar, Ratha Radhakrishna, Purohit Chandra Shekhar
School of Chemical Sciences, National Institute of Science Education and Research (NISER), Jatni, 752050, Bhubaneswar, Odisha, India.
Homi Bhabha National Institute (HBNI), Mumbai, 400 04, Maharashtra, India.
ChemistryOpen. 2025 Sep;14(9):e202500081. doi: 10.1002/open.202500081. Epub 2025 Mar 20.
A 90-membered macrocycle having two functional moiety, diphenyl-phenanthroline (dpp) and two tri-dentate pyridine-diamide (pda) as templating center has been synthesized from precursor molecules via amide bond formation in 10 steps. dpp and pda are arranged alternatively around the macrocycle in a sequence of dpp-pda-dpp-pda and demeostrated orthogonal behaviour, when treated with transition metal such as Cu(I) and Co(III): It forms figure of eight complexes selectively between dpp units and pda units respectively due to the geomtric preferance. This makes the macrocycle operates in bimodal manner. Interconversion between figure of eight complexes has been witnessed by metal-exchange via demetalation and subsequent re-metalation between orthogonal templating centres. Removal of Cu(I) template is performed using a common and less toxic reagent NHCHCHNH and Co(III) by Zn/CHCOOH at RT.
一种具有两个功能部分（二苯基菲咯啉（dpp））和两个三齿吡啶二酰胺（pda）作为模板中心的90元大环化合物，已通过前体分子经10步酰胺键形成反应合成。dpp和pda以dpp-pda-dpp-pda的顺序交替排列在大环周围，当用过渡金属如Cu（I）和Co（III）处理时，表现出正交行为：由于几何偏好，它分别在dpp单元和pda单元之间选择性地形成八字形配合物。这使得大环以双峰方式运行。通过去金属化和随后在正交模板中心之间的再金属化进行金属交换，已观察到八字形配合物之间的相互转化。使用常见且毒性较小的试剂NHCHCHNH去除Cu（I）模板，并在室温下用Zn/CHCOOH去除Co（III）。
