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Systematic Expansion of Supercubane Cores in Manganese Oxo Clusters with Tricarboxylate Ligands
Author(s) -
Okui Yayoi,
Catusanu Florina Aurelia,
Kubota Ryoko,
Kure Bunsho,
Nakajima Takayuki,
Tanase Tomoaki,
Kajiwara Takashi,
Mikuriya Masahiro,
Miyasaka Hitoshi,
Yamashita Masahiro
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100781
Subject(s) - chemistry , manganese , antiferromagnetism , crystallography , crystal structure , benzoic acid , stereochemistry , inorganic chemistry , organic chemistry , physics , condensed matter physics
A novel class of high‐nuclearity Mn 17 and Mn 19 mixed‐valent complexes, [Mn 17 (μ‐O) 12 (μ‐OMe) 2 (μ‐kta) 6 (MeOH) 4 ] ( 1 ), [Mn 17 (μ‐O) 14 (μ‐kta) 6 L 4 ] [L = bpy ( 2a ), phen ( 2b ), 4,7‐Ph 2 phen ( 2c ), dmf ( 3 )], and [Mn 19 (μ‐O) 14 (μ‐kta) 6 (bpy) 6 ]X 3 [X = PF 6 ( 4a ), BF 4 ( 4b )], were synthesized by utilizing Kemp's tricarboxylate ligands (H 3 kta = cis , cis ‐1,3,5‐trimethylcyclohexane‐1,3,5‐tricarboxylic acid). The complexes were characterized by X‐ray crystallography and reveal mineralomimetic Mn 13 supercubane units, [Mn 13 (μ‐O) 14 ], in which their oxidation states systematically altered, depending on their vertex face‐capping ligands and Mn II satellite fragments. Complex 2a was converted by treatment with benzoic acid and [Mn 2 O 2 (bpy) 4 ](BF 4 ) 3 to a cage‐type Mn 14 complex, [Mn 14 (μ‐O) 12 (μ‐OH) 6 (μ‐Hkta) 6 (bpy) 6 ](BF 4 ) 4 ( 5 ), which show ferro‐ and antiferromagnetic interactions and slow magnetic relaxation at low temperature.