Solvent-modulated structures in anilato-based 2D coordination polymers

Tuning the Structure and Properties of Lanthanoid Coordination Polymers with an Asymmetric Anilato Ligand

“…The observed behaviour indicates that compounds 2-4 are essentially paramagnetic and, therefore, also indicates that the chlorocyananilato bridge gives rise to very weak (if any) magnetic coupling, in agreement with the observed behaviour when the anilato-type ligands connect transition metals [27,29,30] or Ln(III) ions [33,36,37]. The observed χ m T values at room temperature are close to those calculated for 3 H 4 (in compounds 2 and 3) or 2 F 7/2 ground multiplets (in compound 4) [44].…”

“…Interestingly, this ligand shows luminescent properties in solid state [40] and in solution [39], as well as in the two Al(III) complexes. Given these above-mentioned results: (i) the luminescence of the nitranilato derivative with Ho(III) [37], (ii) the intrinsic luminescence of the chlorocyananilato ligand [39,40], (iii) the luminescence shown by many Ln(III) ions, (iv) the above-mentioned ability of anilato ligands to form 2D lattices with all the Ln(III) ions [31,33,36] (Tables 1-3), and (v) the capacity shown by some coordinating solvents to modify these 2D lattices [35,36], we have initiated a detailed study to prepare and characterize the complete series of compounds with Ln(III) ions and the ligand chlorocyananilato. Furthermore, we have decided to use different solvents as H 2 O, DMF, and DMSO, since these solvents have a high ability to coordinate to the Ln(III) ions [41], and are therefore expected to modulate not only the luminescent properties, but also the structure of the resulting compounds, as has been very recently demonstrated by some of us [36] …”

“…These three compounds present the same (6,3)-2D topology, but the cavities are rectangular (in the EtOH and DMF cases) or have a very distorted hexagonal shape (in the DMSO compound), suggesting that the solvent plays an important role in the final structure. Thus, the change of water in compound [Er 2 (C 6 O 4 Br 2 ) 3 (H 2 O) 6 ]·12H 2 O to other coordinating solvents, such as DMSO, and DMF, leads to changes in the coordination number and geometry of the metal (nine for H 2 O and DMF vs. eight for DMSO), in the size and distortions of the cavities (hexagonal for H 2 O, distorted hexagonal for DMSO, and rectangular for DMF), in the content of the cavities (12 H 2 O molecules, two DMSO and two H 2 O molecules, or nothing), and even in the interlayer separation [36].…”

Coordinating Ability of Anions, Solvents, Amino Acids, and Gases towards Alkaline and Alkaline‐Earth Elements, Transition Metals, and Lanthanides

“…[24] The preferentialc oordination of DMSO to Zn II in competition with am ethanol-rich mediumh as also been observed, [20] and other cases in whicht he choice of as olvent was made based on its coordinating abilities have also been reported. [25][26][27][28] The reactiono fN i II with at ridentate ligand in DMFy ields a precipitate that, recrystallized in am ixture of DMSO/CH 2 Cl 2 / MeOH in a1 :1:1 ratio results in ab inuclear complex with no methanol or dichloromethane, but with coordinated DMSO, the solvent of the mixture with the highest coordinating ability index. By slow evaporation of the filtrateoft he DMF solution a different, tetranuclear,complexi sobtained that does not incorporate the weaker coordinating solvent DMF.…”

Chloranilato-Based Layered Ferrimagnets with Solvent-Dependent Ordering Temperatures

“…The possibility to change the magnetic properties (ordering temperatures, magnetic behavior, or critical and coercive fields) by simply changing the solvent molecules is, therefore, a very appealing strategy to modulate T c in these series of 2D magnets. Furthermore, when using lanthanoids as metal ions, the solvent molecules also play a key structural role in these (6,3)-2D lattices [24,[29][30][31][32][33][34][35][36][37][38].…”