From Condensed Lanthanide Coordination Solids to Microporous Frameworks Having Accessible Metal Sites

Abstract

The combination of terbium nitrate and 1,4-benzenedicarboxylic acid (H 2 BDC) in the presence of triethylamine yields the compound Tb 2 (BDC) 3 ‚(H 2 O) 4 , which has an extended nonporous structure constructed from copolymerized BDC and Tb(III) units. The multidentate functionality of BDC and the tendency of Tb to have a high coordination number has allowed water to act as a terminal ligand to Tb in the structure. Upon thermally liberating the water ligands, a microporous material, Tb 2 (BDC) 3 , is achieved, which has extended 1-D channels and the same framework structure as that of the as-synthesized solid as evidenced by XRPD. Water sorption isotherm data proves that Tb 2 (BDC) 3 has permanent microporosity, and points to the presence of accessible metal sites within the pores, which also allows the sorption of ammonia to give Tb 2 (BDC) 3 ‚ (NH 3 ) 4 . Luminescence lifetime measurements confirm that resorbed water and sorbed ammonia are bound to Tb and that they give distinctly different decay constants.

Crystal structure of diaquabis(1,10-phenanthroline)dilanthanum(III) tris(μ-1,4-benzenedicarboxylate), La2(H2O)2(C12H8N2)2(C8H4O4)3

“…Recently, lanthanide coordination polymers using phthalic acid by hydrothermal method have been reported, such as complexes [Ln2(bdc)3(H20)]" (Ln = La, Eu, Tb; ifebdc = 1,2-benzenedicarboxylic acid) [1], [Zyi4(mbdc)6(phen)]" (Ln = Tb, Er; H2bdc = 1,3-benzenedicaiboxylic acid; phen = 1,10-phenanthroline) [2], and Tb2(bdc)3(H20)4 (H2bdc = 1,4-benzenedicarboxylic acid) [3], Dimeric units La2(bdc)3(phen)2(H20)2 may be viewed as building blocks of the title crystal structure (H2bdc = 1,4-benzenedicarboxylic acid, phen = 1,10-phenanthroline). Each La(HI) ion is coordinated by five oxygen atoms of bdc 2-dianions, two nitrogen atoms of phen and one oxygen atom of water molecule.…”

Structural Diversity of Five New Lanthanide Coordination Polymers Tuned by Different Salt Anions

“…[16][17][18][19][20][21] Only three lanthanide coordination polymers based on 1,4-H 2 NDC and phen have been reported so far. 21 In Determination of Crystal Structures.…”

Synthesis and characterization of two dimensional metal organic framework of cerium with tetraaza macrocyclic

“…Lanthanides complexes of MOFs are less common compare to their d-bock transition metals due to high coordination number and flexibility of coordination sphere which makes the designation difficult [6,4]. Some lanthanides MOFs have been successfully synthesized in the past few years mainly with Tb, Ho, Er, Yb and Y [8,12]. The MOFs are usually synthesized using hydrothermal method at elevated temperature and may take longer time.…”