Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe2+, Cu2+, Zn2+) with Reversible and Irreversible Adsorptions for Oxygen.

Isolated octanuclear iron-vanadium malate (NH4)3(CH3NH3)3[FeIII2VIV2VV4O11(mal)6]·7.5H2O (1; H3mal = malic acid) and its family of metal hydrates M'3n[MII(H2O)2]1.5n[FeIII2VIV2VV4O11(mal)6]n·xnH2O (2 or 2-Fe, M' = NH4+, M = Fe, x = 7.5; 3 or 3-Cu, M' = K+, M = Cu, x = 10; 4 or 4-Zn, M' = K+, M = Zn, x = 6.5) have been obtained by self-assembly in water. The cluster anion [Fe2V6O11(mal)6]6- (1a) shows an interesting iron bicapped-triangular-prismatic structure, which is bridged by M2+ hydrates (M = Fe, Cu, Zn) to construct isostructural metal organic frameworks (MOFs) 2-4. The mixed-valence vanadium systems in 1-4 were determined by theoretical bond valence calculations (BVS) and charge balance. The magnetic susceptibilities are further elucidated as high spin for Fe3+ in 1a and bridging Fe2+ in 2-Fe, respectively. A strong ferromagnetic interaction was also observed for 2-Fe at 3 K. 2-Fe, 3-Cu, and 4-Zn have similar hydrophilic channels with diameters of 6.8, 6.5, and 6.6 Å, respectively, which show obvious affinity for O2 in comparison with no adsorption of N2, H2, CO2, and CH4 at room temperature under different pressures. Moreover, 2-Fe and 4-Zn exhibit irreversible O2 absorptions, which may be attributed to charge transfer between O2 and open metal sites (OMSs) formed during vacuum heating pretreatment. UV-vis and EPR spectra show a change in electronic structure of 2-Fe after O2 adsorption. The reversible adsorption observed in 3-Cu suggests a weak interaction between O2 and Cu2+ due to the Jahn-Teller effect. The properties of gas adsorption provide an insight into the performances of small molecules in the channels constructed by synthetic octanuclear model compounds, which are related to the interactions between the gas substrate and the heterometal cluster in biology.

Gas Adsorption of Mixed-Valence Trinuclear Oxothiomolybdenum Glycolates.

Trinuclear oxothiomolybdenum(IV) glycolates (H2glyc, glycolic acid) with 2-methylimidazole (2-mim), 4-methylimidazole (4-mim), and sulfite, Na2[MoIV3(µ3-S)(µ2-O)3(glyc)3(2-mim)3]·1.5H2O (1), (4-Hmim)6[MoIV3(µ3-S)(µ2-O)3(glyc)3(4-mim)3]2[MoVIO2(glyc)2] (2), and Na3(4-Hmim)[MoIV3(µ3-S)(µ2-O)3(SO3)(glyc)3(4-mim)]·8H2O (3), have been isolated in reduced media, where 4-methylimidazole trinuclear oxothiomolybdenum(IV) glycolates in 2 coprecipitate with dioxomolybdenum(VI) glycolate, exhibiting unusual mixed valences of 4+ and 6+. Large downfield shifts of glycolates have been observed in solid-state and solution 13C (1H) NMR spectra with coordination to Mo, indicating obvious dissociation of soluble 1 and 3 in solution. Investigations of the coordination modes and conversions among the three complexes give insight into the reactivities of trinuclear oxothiomolybdenum(IV) complexes. Channels with 3.1 × 7.0 Å2 diameters exist in 2, showing reversible O2 absorption of 65.03 mg at 29.9 bar compared with little or no adsorption of N2, H2, CO2, and CH4 at room temperature, respectively. Moreover, trinuclear 2- or 4-methylimidazole oxothiomolybdenum(IV) glycolates 1 and 3 show only a few adsorptions for O2 under the same conditions.

2-Methylimidazole Copper Iminodiacetates for the Adsorption of Oxygen and Catalytic Oxidation of Cyclohexane.

The mixed-ligand copper(II) iminodiacetates [Cu(ida)(2-mim)(H2O)2]·H2O (1), [Cu(ida)(2-mim)2]·2H2O (2), [Cu(ida)(2-mim)(H2O)]n·4.5nH2O (3), and [Cu2(ida)2(2-mim)2]n·nH2O (4) (H2ida = iminodiacetic acid, 2-mim = 2-methylimidazole) were obtained from neutral or alkaline solutions at different temperatures. The novel complex 4 contains very small holes with diameters of 2.9 Å, which can adsorb O2 selectively and reversibly between 1.89 to 29.90 bars, compared with the different gases of N2, H2, CO2, and CH4. This complex is stable up to 150 °C based on thermal analyses and XRD patterns. The four complexes show catalytic activities that facilitate the conversion of cyclohexane to cyclohexanol and cyclohexanone with hydrogen peroxide in a solution. The total conversion is 31% for 4.

Binuclear, tetranuclear and hexadecanuclear thio-oxomolybdenum(V/IV) glycolates with selective adsorptions of gases.

By adjusting the pH values of the solutions, binuclear, tetranuclear and hexadecanuclear glycolato thio- and oxomolybdenum(V/IV) complexes [MoV2O2(µ2-O)(µ2-S)(Hglyc)2(Hpz)2]·H2O (1, H2glyc = glycolic acid, Hpz = pyrazole), (Hdpa)[MoV2O2(µ2-S)2(Hglyc)(glyc)(H2O)] (2, dpa = 2,2'-dipyridylamine), (Hdpa)4[MoV4O4(µ3-O)2(µ2-S)2(glyc)2(S2O3)2] (3) and Na2[MoIV4MoV12O12(µ2-O)6(µ2-OH)2(µ3-O)12(glyc)4(Hpz)4(pz)8]·28H2O (4) have been obtained successfully. Here the glycolates existed in varying aggregates with different degrees of protonation and deprotonation in 1-4. The stable formations of 1 and 2 are attributed to strong hydrogen bonds formed between the molecules. In particular, the asymmetric unit in 2 is a tetramer linked by hydrogen bonding [2.574(9) Å] between α-hydroxy and α-alkoxy groups for further construction of unsaturated penta-coordination environments. Moreover, deprotonated glycolates act as bridging ligands to form tetra- and hexadecanuclear compounds 3 and 4, respectively. The smallest unit in 4 exhibits mixed valences of 4+ and 5+ simultaneously, where its gas adsorption experiments manifest that 4 is obviously beneficial for O2 and CO2 compared with no adsorption of N2, CH4 and H2 at different pressures.

Successive constructions of regular tetra-, hexa- and octanuclear microporous polyoxovanadates(III) for gas adsorption.

Pyrazole-assisted tetranuclear microporous polyoxovanadates(III) (POVs) (NH4)2K2[V4(µ2-OH)4(ox)4(pz)4]·9H2O (1, ox = oxalate and pz = pyrazole) and (NH4)2Na2[V4(µ2-OH)4(ox)4(4-mpz)4]·7H2O (2, 4-mpz = 4-methylpyrazole) have been constructed in reduced media, along with their triazole neutral hexa- and octanuclear products K2[V6(µ2-OH)6(ox)6(Hdatrz)6]Cl2·29.5H2O (3) and [V8(µ2-OH)8(SO3)8(Hdatrz)8]·38H2O (4, Hdatrz = 1H-1,2,4-triazole-3,5-diamine) successively. Both polyanionic structures of 1 and 2 share similar inorganic building blocks that consist of regular {V4(µ2-OH)4} skeletons with an inner diameter of 2.8 Å, while a paddle wheel-shaped cluster 3 contains a {V6(µ2-OH)6} skeleton with two chlorides encapsulated around the center of the ring, occupying a hole of 3.7 Å. An interesting isolated intrinsic polyoxometalate-based metal-organic framework (POMOF) 4 exists as an octanuclear petaloid-like skeleton {V8(µ2-OH)8(SO3)8} with an inner diameter of 5.2 Å. Bond valence sum calculations manifest that all V ions have severely reduced +3 oxidation states in 1-4, which are supported by charge balance, structural and magnetic data. Moreover, gas adsorptions indicate that 1, 2 and 4 can adsorb CO2 and O2 more favorably than N2, CH4 and H2 gases. Compared with 1 and 2, due to the functionalization of microchannels with Lewis base amino and hydroxy groups and uncoordinated azolate N-donors inside POMOF 4, it should have notable affinities toward CO2 adsorption.

Photoinduced Formation of Peroxide Ions on La2O3 and Nd2O3 under O2: Effects of Excitation Wavelength and Crystal Structure.

Photoinduced formation of peroxide ions on La2O3 and Nd2O3 under O2 was studied by in-situ microprobe Raman spectroscopy with attention focused on the effect of excitation wavelength and crystal structure on the O2(2-) formation. It was found that photoexcitations at 633, 532, 514, and 325 nm can induce O2(2-) formation over La2O3 at 450 °C. By contrast, photoexcitation at 785 nm does not cause formation of O2(2-) up to 500 °C. Photoexcitation at 325 nm can induce O2(2-) formation on cubic Nd2O3 at 25 °C, but cannot induce O2(2-) formation on hexagonal Nd2O3 up to 200 °C. The significant difference in the behavior of O2(2-) formation over the Nd2O3 samples of the two structures can be related to the difference in the capacity to adsorb O2. Since the number of oxygen vacancies in cubic Nd2O3 is larger than that in the hexagonal one, the former has a higher capacity than the latter to adsorb O2. As a result, cubic Nd2O3 is more favorable to the reaction of O2 with O(2-) to generate O2(2-). The structural similarity between cubic Nd2O3 and Nd2O2(O2) may be another factor in favor of peroxide formation.