Imidoyl Amidine Ligands: A Versatile Framework to Build Homo and Heterometallic Complexes

Luis Raúl Castañeda-Perea, University, My
2020
Ligand design in general enables the formation of coordination compounds with multiple functionalities within a single framework. To date, two of the most widely studied ligands are 2,2′:6′,2′′-terpyridine (terpy) and acetylacetone (acac), whose tridentate and bidentate coordination pockets, respectively, enables the formation of metallic complexes with various geometries. The Brusso group had been incorporating imidoyl amidine (ImAm) ligands to build different materials such as organic
more » ... and fluorescent materials. In particular, the ligands N-2-pyridylimidoyl-2-pyridylamidine (Py2ImAm) and N-2-pyrimidylimidoyl-2-pyrimidylamidine (Pm2ImAm) were recently synthesized and have great appeal to build metallic complexes, as they poses two coordination sites similar to those in terpy and acac. The work presented herein represents the first studies involving the coordination of Py2ImAm and Pm2ImAm as discrete ligands. Our results demonstrate the versatility of these ligand frameworks, in which discrete mononuclear complexes, homometallic and heterometallic polynuclear complexes may be realized. Chapter one serves as a brief introduction to transition metal chemistry and has a comprehensive review of the coordination chemistry of the ImAm ligand framework. In chapter two, the selective coordination of first row transition metals into the bidentate or tridentate sites of Py2ImAm is explored. The formation of these mononuclear complexes is acid-base driven, where a weak acid induces coordination to the tridentate site and a weak base leads to coordination in the bidentate site. Coordination to both sides of Pm2ImAm with manganese or iron is explored in chapter three. The results show the formation of unusual tetranuclear complexes with the metal ions in both low spin and high spin configurations. Chapter four covers the coordination to cobalt, and the formation of polynuclear complexes with different geometries using Pm2ImAm. The magnetochemistry of these cobalt polynuclear complexes is also presented and reveal a si [...]
doi:10.20381/ruor-24940 fatcat:zw6iu52fqzczdic2ihd3glfjna