RT Journal Article
T1 Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes
A1 Corredoira Vázquez, Julio
A1 González-Barreira, Cristina
A1 Sanmartín Matalobos, Jesús
A1 García Deibe, Ana María
A1 Fondo Busto, María Matilde
K1 N6 macrocycle
K1 Amine ligands
K1 Conformation
K1 Twisting
K1 Dysprosium
K1 Pyridine
K1 Fluorescence
AB Hexaazamacrocyclic Schiff bases have been extensively combined with lanthanoid (Ln) ions to obtain complexes with a highly axial geometry. However, the use of flexible hexaazatetraamine macrocycles containing two pyridines and acyclic spacers is rather uncommon. Accordingly, we obtained [DyL(OAc)2]OAc·7H2O·EtOH and [DyLMe2(Cl)2]Cl·2H2O, where L and LMe2 are the 18-membered macrocycles 3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane and 3,10-dimethyl-3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane, respectively, which contain ethylene and methylethylene spacers between their N3 moieties. [DyL(OAc)2]OAc·7H2O·EtOH represents the first crystallographically characterized lanthanoid complex of L, while [DyLMe2(Cl)2]Cl·2H2O contributes to increasing the scarce number of LnIII compounds containing LMe2. Furthermore, the crystal structure of L·12H2O was solved, and it was compared with those of other related macrocycles previously published. Likewise, the crystal structures of the DyIII complexes were compared with those of the lanthanoid and d-metal complexes of other 18-membered N6 donor macrocycles. This comparison showed some effect of the spacers employed, as well as the influence of the size of the ancillary ligands and the metal ion. Additionally, the distinct folding behaviors of these macrocycles influenced their coordination geometries. Moreover, the luminescent properties of [DyL(OAc)2]OAc·7H2O·EtOH and [DyLMe2(Cl)2]Cl·2H2O were also investigated, showing that both complexes are fluorescent, with the emission being sensitized by the ligands.
PB MDPI
YR 2024
FD 2024
LK https://hdl.handle.net/10347/37723
UL https://hdl.handle.net/10347/37723
LA eng
NO Corredoira-Vázquez, J.; González-Barreira, C.; Sanmartín-Matalobos, J.; García-Deibe, A.M.; Fondo, M. Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes. Int. J. Mol. Sci. 2024, 25, 6802. https://doi.org/10.3390/ ijms25126802
NO This research received no external funding. J.C.-V. thanks Xunta de Galicia for his postdoctoral fellowship (ED481B-2022-068).
DS Minerva
RD 27 abr 2026