TY - JOUR
T1 - Homometallic {Mn10} and heterometallic {Mn6Ca4} supertetrahedra exhibiting an unprecedented {MnIII9MnII} oxidation state level and heterometal ions distribution
AU - Skordi, Katerina
AU - Papatriantafyllopoulou, Constantina
AU - Zartilas, Sotiris
AU - Poole, Katye M.
AU - Nastopoulos, Vassilios
AU - Christou, George
AU - Tasiopoulos, Anastasios J.
N1 - Publisher Copyright:
© 2018 Elsevier Ltd
PY - 2018/9/1
Y1 - 2018/9/1
N2 - Two novel decametallic clusters displaying a supertetrahedral structural core are discussed, a homometallic compound [MnIII9MnII(μ4-O)4(μ3-OMe)3(btH)3(ed)3(PhCO2)6]·6Η2Ο (1·6Η2Ο) (btH3 = (±)-1,2,4-butanetriol; edH2 = 1,2-ethanediol) and a heterometallic one [MnIII6CaII4(μ4-O)4(μ3-Cl)4(pd)6Cl2(MeOH)10] (2) (pdH2 = 1,3-propanediol). In particular complex 1·6Η2Ο is a new member of an extended family of homometallic Mn10 supertetrahedra which exhibits an unprecedented MnIII9MnII oxidation state level. It is based on a supertetrahedral [MnIII9MnII(μ4-O)4]21+ core with its peripheral ligation being completed by bridging alkoxy (OMe−, btH2−, ed2−) and carboxylate (PhCO2−) ligands. Complex 2 is a unique heterometallic analogue of the family of complexes displaying the well-known [MnIII6MnII4(μ4-O)4]18+ supertetrahedral core in which the MnII ions have been replaced by CaII ions. The peripheral ligation of the heterometallic [MnIII6CaII4(μ4-O)4]18+ core is completed by both bridging (μ3-Cl− and pd) and terminal (Cl−, MeOH) ligands. Magnetism studies revealed that complex 1·6Η2Ο displays dominant ferromagnetic exchange interactions and a large spin ground state value ST = 23/2 whereas complex 2 exhibits exclusively ferromagnetic exchange interactions and the maximum possible spin ground state ST = 12 for a complex consisting of six MnIII and four CaII ions.
AB - Two novel decametallic clusters displaying a supertetrahedral structural core are discussed, a homometallic compound [MnIII9MnII(μ4-O)4(μ3-OMe)3(btH)3(ed)3(PhCO2)6]·6Η2Ο (1·6Η2Ο) (btH3 = (±)-1,2,4-butanetriol; edH2 = 1,2-ethanediol) and a heterometallic one [MnIII6CaII4(μ4-O)4(μ3-Cl)4(pd)6Cl2(MeOH)10] (2) (pdH2 = 1,3-propanediol). In particular complex 1·6Η2Ο is a new member of an extended family of homometallic Mn10 supertetrahedra which exhibits an unprecedented MnIII9MnII oxidation state level. It is based on a supertetrahedral [MnIII9MnII(μ4-O)4]21+ core with its peripheral ligation being completed by bridging alkoxy (OMe−, btH2−, ed2−) and carboxylate (PhCO2−) ligands. Complex 2 is a unique heterometallic analogue of the family of complexes displaying the well-known [MnIII6MnII4(μ4-O)4]18+ supertetrahedral core in which the MnII ions have been replaced by CaII ions. The peripheral ligation of the heterometallic [MnIII6CaII4(μ4-O)4]18+ core is completed by both bridging (μ3-Cl− and pd) and terminal (Cl−, MeOH) ligands. Magnetism studies revealed that complex 1·6Η2Ο displays dominant ferromagnetic exchange interactions and a large spin ground state value ST = 23/2 whereas complex 2 exhibits exclusively ferromagnetic exchange interactions and the maximum possible spin ground state ST = 12 for a complex consisting of six MnIII and four CaII ions.
KW - Crystal structures
KW - Ferromagnetic exchange interactions
KW - Magnetic properties
KW - Manganese clusters
KW - Polyols
UR - https://www.scopus.com/pages/publications/85048781276
U2 - 10.1016/j.poly.2018.05.029
DO - 10.1016/j.poly.2018.05.029
M3 - Article
SN - 0277-5387
VL - 151
SP - 433
EP - 440
JO - Polyhedron
JF - Polyhedron
ER -