Heterometallic MnIII4Ln2 (Ln = Dy, Gd, Tb) Cross-Shaped Clusters and Their Homometallic MnIII4MnII2 Analogues.

The employment of di-2-pyridyl ketone, (py)2CO, in heterometallic Mn/4f and homometallic Mn cluster chemistry has yielded six MnIII4Ln2 and two MnIII4MnII2 structurally related clusters, namely, [Mn4Ln2O2{(py)2CO2}4(NO3)2(RCO2)2(H2O)6](NO3)2 (Ln = Gd, 1, 5; Dy, 2; Tb, 3; R = Et, 1-3; Me, 5), [Mn4Dy2O2{(py)2CO2}4(NO3)4(EtCO2)2(H2O)3(MeOH)]·0.7MeOH·0.8H2O (4·0.7MeOH·0.8H2O), [Mn4Gd2O2{(py)2CO2}4(NO3)4(C6H4ClCO2)2(MeOH)2(py)2]·2MeOH (6·2MeOH), [Mn6O2{(py)2CO2}4(py)4(H2O)4](ClO4)4·4H2O (7·4H2O), and [Mn6O2{(py)2CO2}4(NO3)4(py)4] (8), where (py)2CO22- is the dianion of the gem-diol derivative of (py)2CO. The compounds possess a new type of cross-shaped structural core, which in the case of 1-6 is essentially planar, whereas in 7 and 8 it deviates from planarity. Clusters 1-6 are rare examples of Mn/4f species bearing (py)2CO or its derivatives, despite the fact that this ligand has been well-studied and proven a rich source of more than 200 metal compounds so far. Variable-temperature, solid-state direct-current and alternating-current magnetization studies were performed on complexes 1-5, 7, and 8 revealing that the dominant exchange interactions between the metal ions are antiferromagnetic and indicating ground-state spin values of S = 5 (for 1), 6 (for 5), and 2 (for 7 and 8).

Interesting chemical and physical features of the products of the reactions between trivalent lanthanoids and a tetradentate Schiff base derived from cyclohexane-1,2-diamine.

The initial use of a tetradentate Schiff base (LH2) derived from the 2 : 1 condensation between 2-hydroxyacetophenone and cyclohexane-1,2-diamine in 4f-metal chemistry is described. The 1 : 2 reaction of Ln(NO3)3·xH2O (Ln = lanthanoid or yttrium) and LH2 in MeOH/CH2Cl2 has provided access to isostructural complexes [Ln(NO3)3(L'H2)(MeOH)] in moderate to good yields. Surprisingly, the products contain the corresponding Schiff base ligand L'H2 possessing six aliphatic -CH2- groups instead of the -CH-(CH2)4-CH- unit of the cyclohexane ring, i.e. an unusual ring-opening of the latter has occurred. A mechanism for this LnIII-assisted/promoted LH2 → L'H2 transformation has been proposed assuming transient LnII species and a second LH2 molecule as the H2 source for the reduction of the cyclohexane moiety. DFT calculations provide strong evidence for the great thermodynamic stability of the products in comparison with analogous complexes containing the original intact ligand. The structures of the PrIII, SmIII, GdIII, TbIII, and HoIII complexes have been determined by single-crystal X-ray crystallography. The 9-coordinate LnIII centre in the molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the bidentate chelating organic ligand, and one oxygen atom from the coordinated MeOH group. In the overall neutral bis(zwitterionic) L'H2 ligand, the acidic H atoms are clearly located on the imino nitrogen atoms and this results in the formation of an unusual 16-membered chelating ring. The coordination polyhedra defined by the nine donor atoms around the 4f-metal-ion centres can be best described as distorted, spherical capped square antiprisms. The EuIII, TbIII, and DyIII complexes exhibit LnIII-based luminescence in the visible region, with the coordinated L'H2 molecule acting as the antenna. Ac magnetometry experiments show that the DyIII member of the family behaves as an SIM at zero field and under external dc fields of 0.1 and 0.2 T without the enhancement of the peaks' maxima, suggesting that QTM is not the relaxation path. The GdIII complex behaves, rather unexpectedly, as a SIM with two different magnetic relaxation paths occurring at very close temperatures; this behaviour is tentatively attributed to a very small axial zero-field splitting (D ∼ 0.1 cm-1), which cannot be detected by magnetization or susceptibility experiments. The prospects of the present, first results in the lanthanoid(III)-LH2 chemistry are discussed.

Expanding the NUIG MOF family: synthesis and characterization of new MOFs for selective CO2 adsorption, metal ion removal from aqueous systems, and drug delivery applications.

Metal organic frameworks (MOFs) have attracted considerable attention in recent years due to their use in a wide range of environmental, industrial and biomedical applications. The employment of benzophenone-4,4'-dicarboxylic acid (bphdcH2) in MOF chemistry provided access to the 3D mixed metal MOFs [CoNa2(bphdc)2(DMF)2]n (NUIG2) and [ZnK2(bphdc)2(DMF)2]n (NUIG3), and the 2D homometallic MOF [Co2(OH)(bphdcH)2(DMF)2(H2O)2]n(OH)·DMF (1·DMF). 1·DMF is based on a dinuclear SBU and consists of interpenetrating networks with an sql topology. Dc magnetic susceptibility studies were carried out in 1·DMF and revealed the presence of weak antiferomagnetic exchange interactions between the metal centres. NUIG2 and NUIG3 are structural analogues of [ZnNa2(bphdc)2(DMF)2]n (NUIG1), which has shown an exceptionally high encapsulation for ibuprophen (Ibu), NO and metal ions. Both NUIG2 and NUIG3 display high metal ion (CoII, NiII, CuII) adsorption capacity, comparable to that of NUIG1, with NUIG2 exhibiting good performance in Ibu uptake (780 mg Ibu per g NUIG2). Monte Carlo simulations were conducted in NUIG1 in order to assess its adsorption capacity for other guest molecules, and revealed that it possesses an outstanding CO2 uptake at ambient pressure, which is larger than that of the previously reported best functioning species (104 vs. 100 cm3 (stp) per cm3). Furthermore, NUIG1 exhibits high selectivity for CO2 over CH4.

High nuclearity structurally - related Mn supertetrahedral T4 aggregates.

The simultaneous employment of 1,3-propanediol and di-2-pyridyl ketone in Mn carboxylate chemistry has provided access to three new, structurally-related [Mn24] and [Mn23] clusters. They are based on nanosized supertetrahedal T4 Mn/O structural cores and exhibit slow relaxation of magnetization below 3.5 K.

From 1D Coordination Polymers to Metal Organic Frameworks by the Use of 2-Pyridyl Oximes.

The synthesis and characterization of coordination polymers and metal-organic frameworks (MOFs) has attracted a significant interest over the last decades due to their fascinating physical properties, as well as their use in a wide range of technological, environmental, and biomedical applications. The initial use of 2-pyridyl oximic ligands such as pyridine-2 amidoxime (H2pyaox) and 2-methyl pyridyl ketoxime (Hmpko) in combination with 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), H4pma, provided access to nine new compounds whose structures and properties are discussed in detail. Among them, [Zn2(pma)(H2pyaox)2(H2O)2]n (3) and [Cu4(OH)2(pma)(mpko)2]n (9) are the first MOFs based on a 2-pyridyl oxime with 9 possessing a novel 3,4,5,8-c net topology. [Zn2(pma)(H2pyaox)2]n (2), [Cu2(pma)(H2pyaox)2(DMF)2]n (6), and [Cu2(pma)(Hmpko)2(DMF)2]n (8) join a small family of coordination polymers containing an oximic ligand. 9 exhibits selectivity for FeIII ions adsorption, as was demonstrated by a variety of techniques including UV-vis, EDX, and magnetism. DC magnetic susceptibility studies in 9 revealed the presence of strong antiferromagnetic interactions between the metal centers, which lead to a diamagnetic ground state; it was also found that the magnetic properties of 9 are affected by the amount of the encapsulated Fe3+ ions, which is a very desirable property for the development of magnetism-based sensors.