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Metallacrowns as Templates for Diabolo‐like {LnCu 8 } Complexes with Nearly Perfect Square Antiprismatic Geometry
Author(s) -
Zhou GuoJun,
Han Tian,
Ding YouSong,
Chilton Nicholas F.,
Zheng YanZhen
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703830
Subject(s) - lanthanide , ion , crystallography , coordination geometry , geometry , ideal (ethics) , ligand (biochemistry) , relaxation (psychology) , chemistry , square (algebra) , symmetry (geometry) , molecule , lone pair , crystal structure , social psychology , psychology , hydrogen bond , philosophy , receptor , mathematics , biochemistry , organic chemistry , epistemology
A series of diabolo‐like nonanuclear {Ln III Cu II 8 } (Ln=Tb, Dy, Ho, Er, Tm, Yb, and Y) clusters were prepared in which the Ln III ion is capped by two 8‐MC‐4 metallacrown ligands to form a nearly ideal square antiprismatic (SAP) coordination geometry with D 4 d symmetry. Despite the lack of crystallographic symmetry, these molecules engender the lanthanide ions with highly axial m J states. The axial/equatorial nature of the crystal field in environments close to ideal SAP geometry is very subtle and influenced by the nature of the ligand lone pairs. Slow magnetic relaxation behaviour was observed for the Dy III , Er III , Tm III , and Yb III analogues, and the obtained effective energy barriers are not consistent with excitations on the Ln III ion, suggesting a more nuanced situation.