A Robust Open Framework Formed by Decavanadate Clusters and Copper(II) Complexes of Macrocyclic Polyamines: Permanent Microporosity and Catalytic Oxidation of Cycloalkanes.
The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1, cyclam = 1,4,8,11-tetraazacyclotetradecane) was prepared by reaction of (VO3)(-) anions and {Cu(cyclam)}(2+) complexes in NaCl (aq) at pH 4.6-4.7 and characterized by elemental analyses, thermogravimetry, and X-ray diffraction (powder, single-crystal) techniques. Compound 1 exhibits a POMOF-like supramolecular open-framework built of covalent decavanadate/metalorganic layers with square-like voids, the stacking of which is aided by interlamellar cementing complexes and generates water-filled channels with approximate cross sections of 10.4 × 8.8 Å(2). The framework is robust enough to remain virtually unaltered upon thermal evacuation of all water molecules of hydration, as demonstrated through single-crystal X-ray diffraction studies on the anhydrous phase 1a. This permanent microporosity renders interesting functionality to 1, such as selective adsorption of CO2 over N2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly-stable, tricyclic alkane adamantane.
BCMaterials , Edificio 500, Parque Tecnológico de Bizkaia, 48160 Derio, Spain.
Jagoba
J
Martín-Caballero
Departamento de Desarrollo Sostenible, Universidad Católica de Ávila , c/Canteros s/n, 05005 Ávila, Spain.
Ana
A
San José Wéry
Santiago
S
Reinoso
BCMaterials , Edificio 500, Parque Tecnológico de Bizkaia, 48160 Derio, Spain.
Beñat
B
Artetxe
Leire
L
San Felices
Grupo de Materiales Carbonosos y Medio Ambiente, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Alicante , P.O. Box 99, 03080 Alicante, Spain.
Bouchra
B
El Bakkali
Grupo de Materiales Carbonosos y Medio Ambiente, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Alicante , P.O. Box 99, 03080 Alicante, Spain.
Guido
G
Trautwein
Grupo de Materiales Carbonosos y Medio Ambiente, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Alicante , P.O. Box 99, 03080 Alicante, Spain.
Juan
J
Alcañiz-Monge
BCMaterials , Edificio 500, Parque Tecnológico de Bizkaia, 48160 Derio, Spain.
José Luis
JL
Vilas
BCMaterials , Edificio 500, Parque Tecnológico de Bizkaia, 48160 Derio, Spain.
Juan M
JM
Gutiérrez-Zorrilla