Synthesis and Characterization of Novel Cobalt Carbonyl Phosphorus and Arsenic Clusters.

Phosphorus- and arsenic-containing cobalt clusters are an interesting class of compounds that continue to provide new structures with captivating bonding patterns. Although the first members of this family were reported 45 years ago, the number of such species is still limited within the broad family of transition metal complexes bearing pnictogen atoms. Herein, we present the reaction of Co2(CO)8 as a cobalt source with a number of phosphorus- and arsenic-containing compounds under variable reaction conditions. These reactions result in various known and novel cobalt phosphorus and cobalt arsenic clusters in which different nuclearity ratios between P/As and Co exist. All those clusters were characterized by X-ray structural analysis and partly by IR, 31P{1H} NMR, EI-MS and elemental analysis. This comprehensive study is the first detailed study in this field that reveals the richness of compounds that could be obtained only by modifying the ratio of used reactants and the involved reaction conditions.

Windmill Co4 {Co4 (µ4 -O)} with 16 Divergent Branches Forming a Family of Metal-Organic Frameworks: Organic Metrics Control Topology, Gas Sorption, and Magnetism.

A series of highly connected metal-organic frameworks (MOFs), [Co8 (O)(OH)4 (H2 O)4 (ina)8 ](NO3 )2 ⋅2 C2 H5 OH⋅4 H2 O (1), [Co8 (O)(OH)4 (H2 O)4 (pba)8 ](NO3 )2 ⋅8 C2 H5 OH⋅28 H2 O (2), and [Co8 (O)(OH)4 (H2 O)4 (pbba)8 ](NO3 )2 ⋅guest (3), in which ina=isonicotinate, pba=4-pyridylbenzoate, and pbba=4-(pyridine-4-yl)phenylbenzoate, is reported. These MOFs contain a new secondary building unit (SBU), with a square Co4 (µ4 -O) central unit having the rare µ4 -O(2-) motif, which is decorated by the other four peripheral cobalt atoms through µ3 -OH in a windmill-like shape. This SBU holds 16 divergent connecting organic ligands, pyridyl-carboxylates, to form three different frameworks. The high porosity of desolvated 2 is shown by the efficient gas absorption of N2 , CO2 , CH4 , and H2 . In addition, 1 and 2 exhibit unusual canted antiferromagnetic behavior with spin-glass-like relaxation, with blocking temperatures that are fairly high, 20 K (1) and 10 K (2), for cobalt materials. The relationship between the metal clusters and linkers has been studied, in which the size and rotational degrees of freedom of the ligands are found to control the topology, gas sorption, and magnetic properties.

Electronic structure and reactivity indexes of cobalt clusters, both pure and mixed with NO and [Formula: see text] ([Formula: see text], [Formula: see text] and [Formula: see text]).

Among the most popular motivations for environmental scientists is improving materials that could be useful to fight or avoid pollution. This work shows a study of neutral and cationic cobalt clusters from 4 to 9 atoms ([Formula: see text], q = 0,1 and n = 4-9) to model their separate interaction with contaminant nitric and nitrous oxides. This study is within the framework of the density functional theory in the Kohn-Sham scheme by using BPW91 functional and 6-311G and 6-31G* basis sets to calculate global and local reactivity indexes. The effect of spin multiplicity is also determined. Results on the geometries of pure cobalt clusters agree with previously reported structures. Global minimum energy structures showed a marked preference towards the interaction of nitric and nitrous oxide molecules with cobalt clusters through chemisorptive dissociation, with the dissociation of the corresponding nitrogen oxide. Reactivity indexes reveal an even-odd alternate, which is related to electron counts. Moreover, the chemical potential is lowering after interaction with nitrogen oxides. The Fukui function illustrates the reactive zones with a high probability of chemisorption of more nitrogen oxide molecules.

Two Six-Connected MOFs with Distinct Architecture: Synthesis, Structure, Adsorption, and Magnetic Properties.

By assembling CoII ions and a combination of 5-(4-pyridyl)tetrazole (4-ptz) and formate ions, two distinct metal-organic frameworks, [Co3 (4-ptz)5 (HCOO)(H2 O)2 ] and [Co3 (4-ptz)4 (dmf)2 (HCOO)2 ] (dmf=N,N'-dimethylformamide), were synthesized. They were both characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Structural analyses revealed that by slightly modulating the coordination environment of the trinuclear cobalt cluster, two complexes were formed featuring unusual six-connected nets reminiscent of a pyrazole-type linear trinuclear cobalt cluster as compared with the classic eight-connected bcu topology. In addition, [Co3 (4-ptz)5 (HCOO)(H2 O)2 ] interacted strongly with CO2 , with an adsorption enthalpy of 29.2 kJ mol-1 , and in a selectivity study, the uptake ratios of CO2 /N2 (from a 15:85 mixture) and CO2 /CH4 (50:50 mixture) were 77.6 and 37.7, respectively. Magnetic studies on both complexes revealed weak antiferromagnetic coupling between the CoII ions.