Stepwise self-assembly processes using new lanthanide metalloligands (Ln-MLs) and silver salts have been successfully applied to isolate 4f-4d heterometallic coordination networks of four different structural types. In particular, the new lanthanide tetrakis-chelate complexes NEt4[Ln(L1)4] [HL1 = 1,3-bis(4′-cyanophenyl)-1,3-propanedione; Ln = Eu (1a), La (1b), Nd (1c), Tb (1d)] and NEt4[Ln(L2)4] (HL2 = 1,3-bis(4′-pyridyl)-1,3-propanedione; Ln = Eu (1e), Nd (1f)] have been synthetized, characterized and reacted with different silver salts. The use of NEt4[Ln(L1)4] allowed then to isolate and characterize i) neutral one-dimensional ladder-like species of formula [Ln(L1)4Ag] [Ln = Eu (2a), La(2b), Nd(2c), Tb(2d)] and ii) their supramolecular isomers [Ln(L1)4Ag] [Ln = Eu (3a), La (3b), Nd (3c), Tb (3d)] showing a very unstable 2D network structure, iii) the cationic 2D species [Ln(L1)4Ag2]X [Ln = Eu, X = PF6‾, CF3SO3‾, ClO4‾ (4a–4c); Ln = Tb, Nd, La X = PF6‾ (4d–4f)] and, only for lanthanum, iv) a fourth 2D species of formula [La(L1)4(H2O)Ag] (5) and sql topology. Of the eight nitrile groups on the MLs potentially coordinating, only a partial number is used for networking with Ag(I), that is, only two in families 2 and 3, and four in family 4 and in network 5. Finally, the four structural types are rationalized in terms of a new “pincer-like” Secondary Building Unit (SBU) consisting of a silver cation coordinating two central carbon atoms ( carbon) of two different diketonate ligands on the same ML. Therefore, it is shown that compounds 5, 4 and 2–3 contain, respectively, none, one or two of such pincer-like SBUs. The luminescence properties of the Ln-MLs and some of their polymeric species have been also investigated in solution and in the solid state.
New lanthanide metalloligands and their use for the assembly of Ln-Ag bimetallic coordination frameworks : stepwise modular synthesis, structural characterization, and optical properties / M. Visconti, S. Maggini, G. Ciani, P. Mercandelli, B. Del Secco, L. Prodi, M. Sgarzi, N. Zaccheroni, L. Carlucci. - In: CRYSTAL GROWTH & DESIGN. - ISSN 1528-7483. - 19:9(2019 Sep 04), pp. 5376-5389.
|Titolo:||New lanthanide metalloligands and their use for the assembly of Ln-Ag bimetallic coordination frameworks : stepwise modular synthesis, structural characterization, and optical properties|
VISCONTI, MARCO (Primo)
MAGGINI, SIMONA (Secondo)
CARLUCCI, LUCIA (Ultimo) (Corresponding)
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Progetto:||Highly absorptive microporous materials for gas storage and separation|
|Data di pubblicazione:||4-set-2019|
|Data ahead of print / Data di stampa:||25-lug-2019|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1021/acs.cgd.9b00894|
|Appare nelle tipologie:||01 - Articolo su periodico|