Rational Design of Tetranuclear Complexes Employing N‐Imidoylamidine Based Ligands. Issue 7 (30th January 2019)

• Record Type: Journal Article
• Authors: Castañeda, Raúl; Harriman, Katie L. M.; Wong, Joanne W. L.; Gabidullin, Bulat; Murugesu, Muralee; Brusso, Jaclyn L.
• Is Part Of: European journal of inorganic chemistry. Issue 7(2019)
• Page Start: 963
• Page End: 972
• Publication Date: 2019-01-30
• Subjects: Ligand design -- Coordination modes -- N ligands -- Polynuclear complexes -- Magnetic properties; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201801412
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Ligands such as N ‐2‐pyrimidylimidoyl‐2‐pyrimidylamidine (Pm2 ImAm ) possess both a bidentate and tridentate coordination site within a single ligand framework. Taking advantage of this, two tetranuclear complexes with manganese ([Mn III Mn II 3 (Pm2 ImAm)3 Cl6 ] ) and iron ([Fe III 4 (Pm2 ImAm)3 Cl9 ] ) have been isolated, characterized by single‐crystal X‐ray analysis, and their magnetic properties have been investigated through SQUID magnetometry and Mössbauer spectroscopy. As well, a mononuclear ([Fe III (Pm2 ImAm)Cl3 ] ) and binuclear ([Mn II 2 ( µ ‐Cl)2 (Pm2 ImAm)2 Cl2 ] ) complex employing this ligand framework were also isolated, characterized by single‐crystal X‐ray analysis and their magnetic properties were investigated. For comparison purposes, the previously reported mononuclear complexes [Mn III (Py2 ImAm)3 ] and [Fe III (Py2 ImAm)3 ] were also probed here via SQUID magnetometry due to the similarities between these mononuclear systems and fragments of the tetranuclear complexes. Through this approach, clear interpretation of the magnetic properties in [Mn III Mn II 3 (Pm2 ImAm)3 Cl6 ] and [Fe III 4 (Pm2 ImAm)3 Cl9 ] was achieved. These results reveal that employing our N ‐imidoylamidine ligands facilitates the rational design of polynuclear complexes with differing metal ion spin states. Abstract : Rational design of tetranuclear complexes with manganese and iron was achieved by employing N ‐imidoylamidine ligands. Evaluation via SQUID magnetometry and Mössbauer spectroscopy reveal a unique combination of low and high spin states for the metal centers within these cluster aggregates.