Modulation of the Slow Relaxation of the Magnetization Dynamics through Second Coordination Sphere in Macrocyclic Dysprosium(III) Complexes

Rotondo, Elisa; Aragon-Alberti, Maxime; Rouquette, Jérôme; Long, Jérôme

doi:10.1021/acs.cgd.3c01401

Cited by 1 publication

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References 57 publications

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“…Therefore, we compared the structure adopted in each complex with that assumed for a regular hexagonal disposition of the six N donor atoms, as a function of their ionic radius [ 33 , 34 , 35 ], as it is known that a different degree of distortion in the macrocycles can cause affection of other properties [ 39 ]. This type of theoretical study has been satisfactorily applied to determine the relationship between the transversal magnetic anisotropy and the distortion of a hexaazamacrocycle from planarity [ 40 ] or to find the most appropriate size to fit inside the 18-crown-6 ether cavity [ 41 ]. This latter D 3d planar cavity has a diameter of 5.8 Å, while for 6aa, it is 5.5 Å [ 32 ].…”

Section: Resultsmentioning

confidence: 99%

Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes

Corredoira-Vázquez,

González-Barreira,

Sanmartín-Matalobos

et al. 2024

IJMS

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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.

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