Autor(es):
Shi, Fa-Nian 
; Cunha-Silva, Luis ; Trindade, Tito ; Paz, Filipe A. Almeida ; Rocha, Joao
Data: 2009
Identificador Persistente: http://hdl.handle.net/10773/6221
Origem: RIA - Repositório Institucional da Universidade de Aveiro
Descrição
Three-dimensional lanthanide-organic frameworks formulated as (CH3)2NH2[Ln(pydc)2] · 1/2H2O [Ln3+ ) Eu3+ (1a)
or Er3+ (1b); pydc2- corresponds to the diprotonated residue of 2,5-pyridinedicarboxylic acid (H2pydc)], [Er4(OH)4(pydc)4(H2O)3] ·H2O
(2), and [PrIII
2PrIV
1.25O(OH)3(pydc)3] (3) have been isolated from typical solvothermal (1a and 1b in N,N-dimethylformamide -
DMF) and hydrothermal (2 and 3) syntheses. Materials were characterized in the solid state using single-crystal X-ray diffraction,
thermogravimetric analysis, vibrational spectroscopy (FT-IR and FT-Raman), electron microscopy, and CHN elemental analysis.
While synthesis in DMF promotes the formation of centrosymmetric dimeric units, which act as building blocks in the construction
of anionic ∞
3{[Ln(pydc)2]-} frameworks having the channels filled by the charge-balancing (CH3)2NH2
+ cations generated in situ by
the solvolysis of DMF, the use of water as the solvent medium promotes clustering of the lanthanide centers: structures of 2 and 3
contain instead tetrameric [Er4(μ3-OH)4]8+ and hexameric Pr6(μ3-O)2(μ3-OH)6 clusters which act as the building blocks of the networks,
and are bridged by the H2-xpydcx- residues. It is demonstrated that this modular approach is reflected in the topological nature of
the materials inducing 4-, 8-, and 14-connected uninodal networks (the nodes being the centers of gravity of the clusters) with
topologies identical to those of diamond (family 1), and framework types bct (for 2) and bcu-x (for 3), respectively. The
thermogravimetric studies of compound 3 further reveal a significant weight increase between ambient temperature and 450 °C with
this being correlated with the uptake of oxygen from the surrounding environment by the praseodymium oxide inorganic core.
