Design, synthesis and characterization of a Pt–Gd metal–organic framework containing potentially catalytically active sites

Abstract

The heterobimetallic metal-organic framework {[(BPDC)PtCl(2)](3)(Gd(H(2)O)(3))(2)}.5H(2)O (BPDC = 2,2'-bipyridine-5,5'-dicarboxylate) has been designed and synthesized by hydrothermal methods. The new coordination polymer contains subunits of (BPDC)PtCl(2) (1) where both N atoms of the BPDC ligand are attached to a square-planar Pt(II) center. The two remaining cis coordination sites at Pt(II) are occupied by chloride ions. The final structure (2) of the polymeric network is obtained when Gd(III) ions link together the (BPDC)PtCl(2) units, which are organized in sheets, into larger blocks. These blocks are stacked along the crystallographic [010] direction and are held together by a hydrogen bonding scheme that involves carboxylate oxygen atoms and water molecules in the coordination sphere of Gd. The coordination polymer 2 can be obtained in a single-step reaction or in a two-step synthesis where the corresponding Pt complex (1) was first synthesized followed by reacting 1 with Gd(NO(3))(3).6H(2)O. In situ high temperature powder X-ray diffraction shows that the crystalline coordination polymer transforms into an anhydrous modification at 100 degrees C. This modification is stable to 350 degrees C, at which temperature the structure starts to decompose. The coordination sphere around platinum in the polymer closely resembles organometallic Pt complexes that have been previously found to catalytically or stoichiometrically activate and functionalize hydrocarbon C-H bonds in homogeneous systems.

Syntheses of Metal-organic Framework Compounds Containing Ni-bipyridyl Complex for Oligomerization of Ethylene

“…_ Gd metal-organic framework compound; Gd acts as the corner cation and Pt forms a complex with the bipyridine dicarboxylate unit 12) . We have no definite idea about the structure of Figure 6(a) indicates that the total weight decrease was 64%, with a very sharp fall at about 400 , suggesting that the stoichiometry of Ni to bpydc is close to unity.…”

One-pot syntheses, structures and properties of two novel 1-D copper complexes: [CuII2(Hbpdc)2Cl2]2·2H2O and CuI(H2bpdc)Cl (H2bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid)

“…Currently, the most commonly used N-heterocyclic carboxylic ligands mainly include pyridinecarboxylic acids [3-5], terpyridinecarboxylic acids [6], imidazolecarboxylic acids [7,8], triazolecarboxylic acids [9]. Although 2,2′-bipyridyl-4,4′-dicarboxylic acid as a polydentate ligand has been extensively exploited [10][11][12][13][14][15][16][17], investigations on 2,2′-bipyridyl-5,5′-dicarboxylic acid (H 2 bpdc) as a multifunctional ligand remain largely unexplored [18][19][20][21][22][23][24][25]. Obviously, most of reported metal complexes are the noble metal derivatives, which provides us an excellent opportunity for exploring the reaction of the first-row transition-metal/lanthanide cations with H 2 bpdc based on the following considerations: (a) the flexible multifunctional H 2 bpdc with N and O donor atoms can provide the large possibility for constructing novel structures; (b) H 2 bpdc can be deprotonated to generate Hbpdc − and bpdc 2− , allowing various acidity-dependent coordination modes; and (c) first-row transition-metal cations have a strong affinity to both N-and O-donors while lanthanide cations prefer O-donors to N-donors according to the hard-soft acid base rule.…”

Designing Heterogeneous Catalysts by Incorporating Enzyme-Like Functionalities into MOFs

“…We therefore directed our search towards more robust MOF materials. Replacing zinc with gadolinium resulted in a Pt-containing MOF with a much higher chemical stability [35][36][37]. Figure 13 shows the Creating catalytic activity in MOF structures by modification of the linker.…”