Electrodeposition of layered manganese oxide nanocomposites intercalated with strong and weak polyelectrolytes

Multilayered manganese oxide nanocomposites intercalated with strong (poly(diallyldimethylammonium) chloride, PDDA) and weak (poly(allylamine hydrochloride), PAH) polyelectrolytes can be produced on polycrystalline platinum electrode in a thin film form by a simple, one-step electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn2+ ions at around +1.0 V (vs Ag/AgCl) in the presence of polyelectrolytes. Fully charged PDDA polycations are accommodated tightly in the interlayer space by electrostatic interaction with negative charges on the manganese oxide layers, leading to an interlayer distance of 0.97 nm. The layered film prepared with PAH has a larger polymer content (PAH/Mn molar ratio of 0.98) than that (PDDA/Mn molar ratio of 0.43) made with PDDA because of the smaller charging degree of PAH, exhibiting a larger interlayer distance (1.19 nm). The interlayer PAH contains neutral (-NH2) and positively charged (-NH3(+)) amine groups, and the -NH3(+) groups are associated with Cl- (to generate -NH3(+) Cl- ion pairs) as well as the negatively charged manganese oxide layers. Both polyelectrolytes once incorporated were not ion exchanged with small cations in solution. The layered structure of PDDA/MnO(x) was collapsed during the reduction process in a KCl electrolyte solution, accompanying an expansion of the interlayer as a result of incorporation of K+ ions for charge neutrality. On the contrary, the layered PAH/MnO(x) film showed a good electrochemical response due to the redox reaction of Mn3+/Mn4+ couple with no change in the structure. X-ray photoelectron spectroscopy revealed that, in this case, excess negative charges generated on the manganese oxide layers upon reduction can be balanced by the protons being released from the -NH3(+) Cl- sites in the interlayer PAH; the Cl- anions becoming unnecessary are inevitably excluded from the interlayer, and vice versa upon oxidation.     

Immobilization of methylviologen between well-ordered multilayers of manganese oxide during their electrochemical assembly

Methylviologen dications (MV2+) were immobilized between layers of manganese oxide during their electrochemical assembly by an anodic route in a homogeneous aqueous Mn2+ solution. This approach yielded a well-ordered multilayer film on a platinum substrate as a result of dense packing of planar MV2+ molecules to stabilize the layered framework. A grazing angle in-plane X-ray diffraction study revealed that the manganese oxide sheets and the molecular planes of inserted MV2+ ions are oriented parallel to the electrode surface. Cyclic voltammetry of the product film indicated an electron transfer from the underlying Pt substrate to inserted methylviologen ions through the manganese oxide sheets.     

Redoxable nanosheet crystallites of MnO2 derived via delamination of a layered manganese oxide

This paper reports on the swelling and exfoliation behavior of a layered protonic manganese oxide, H(0.13)MnO(2).0.7H(2)O, in a solution of tetrabutylammonium (TBA) hydroxide and the formation and characterizations of unilamellar two-dimensional crystallites of MnO(2). At low doses of TBA ions, layered manganese oxide was observed to undergo normal intercalation, yielding a TBA intercalated phase with a gallery height of 1.25 nm. With a large excess of TBA ions, osmotic swelling occurred, giving rise to a very large intersheet separation of 3.5-7 nm. In an intermediate TBA concentration range, the sample exhibited a broad X-ray diffraction profile with superimposed diffraction features due to intercalation and osmotic swelling. The component responsible for the broad profile was isolated by centrifuging the mixture twice at different speeds, and the recovered colloid was identified as a pile of MnO(2) nanosheets, corresponding to the individual host layer of the precursor layered manganese oxide. Observations by transmission electron microscopy and atomic force microscopy revealed high two-dimensional anisotropy with a lateral dimension of submicrometers and a thickness of approximately 0.8 nm. The nanosheet exhibited broad optical absorption with a peak at 374 nm (epsilon = 1.13 x 10(4) mol(-1) dm(3) cm(-1)). The restacking process of the colloidal MnO(2) nanosheets was followed by aging the colloid at a relative humidity of 95%. The broad diffraction pattern due to the exfoliated sheets weakened with time and eventually resolved into two sharp distinct profiles attributable to a TBA intercalation compound with an intersheet spacing of 1.72 nm and an osmotically swollen hydrate with >10 nm at a very early stage. As drying progressed, the former phase became more abundant without a change in interlayer distance, while the degree of swelling of the latter phase gradually decreased to 2.7 nm that remained unchanged on further aging. Subsequent drying at a lower humidity collapsed the 2.7 nm phase. The resulting single 1.72 nm phase was dehydrated by heating at 150 degrees C to produce a phase with a contracted interlayer spacing of 1.3 nm.     

A direct electrochemical route to construct a polymer/manganese oxide layered structure

A layered nanocomposite with poly(diallyldimethylammonium), PDDA, intercalated between manganese oxide layers can be formed on a platinum electrode in a thin film form through a direct electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn(2+) precursors in the presence of PDDA by applying a constant potential (+1.0 V vs Ag/AgCl).     

Preparation and formation mechanism of a n-butylammonium/MnO2 layered hybrid via a one-pot synthesis under moderate conditions

The preparation of organic/inorganic layered hybrids has relied on multistep processing. Thus, shortening the synthetic procedure is important for possible future applications, but only a few studies report one-pot syntheses. In this work, we established a simple one-pot solution process to synthesize layered alkyl ammonium/MnO(2) hybrids, by stirring MnCl(2) and alkyl amine/H(2)O(2) aqueous solutions at 40 °C; the reaction concept is a chemical oxidation of Mn(II) ions in the presence of alkyl amine in aqueous solution. Furthermore, the formation mechanism of the layered n-butylammonium/MnO(2) hybrid was examined by following the structural and optical changes during the reaction, revealing that the one-pot reaction includes 3 steps; formation of β-MnOOH, topotactic oxidation of β-Mn(III)OOH to form the protonated layered manganese oxide H(x)Mn(III, IV)O(2)·yH(2)O, and ion-exchange of interlayer H(+) (or H(3)O(+)) with n-butylammonium to form layered n-butylammonium/MnO(2).     

Local structure of Mn4+ and Fe3+ spin probes in layered LiAlO2 oxide by modelling of zero-field splitting parameters

The zero-field splitting parameters (ZFS) of Mn(4+) and Fe(3+) ions in LiAlO(2) with a layered structure are analyzed experimentally and theoretically by using high-frequency electron paramagnetic resonance spectroscopy, Neuman superposition model (NSM), DFT and multiconfigurational calculations. The interpretation of ZFS is based on the comparison of the experimentally determined values with the calculated ones. This approach allows assessing the performance of different methods for computation of ZFS of Fe(3+) and Mn(4+) in layered oxide matrices. DFT and multiconfigurational calculations are used to analyze the effect of oxygen, aluminium, and lithium neighbours on ZFS of Fe(3+) and Mn(4+). These calculations are based on a cluster comprising Fe(3+) or Mn(4+) ions in a trigonally compressed octahedron with 6 metal ions (Al(3+) or Co(3+)) as first metal neighbours and 6 O(2-) and 2 Li(+) (above and below the layer) as second neighbours. A satisfactory agreement with the experimental data is achieved when the local structure of Mn(4+) and Fe(3+) deviates from the trigonal host-site geometry. The local structure of Fe(3+) comprises an axial distortion, while trigonal environment with reduced extent of distortion appears around Mn(4+).     

Intercalation of cobaltammine complex ions into layered manganese oxide

The intercalation of Co(2+), [Co(NH(3))(6)](3+), and [Co(NH(3))(5)Cl](2+) ions into layered manganese oxide (birnessite) was studied by chemical, XRD, SEM, IR, and DTA-TG analyses. The intercalation reaction progressed by a 2:1 or 3:1 ion-exchange mechanism depending on the valence of the starting ions. The oxidation state of cobalt did not change with the intercalation reaction. The intercalation of [Co(NH(3))(6)](3+) ions resulted in an increase of basal spacing from 0.716 to 0.956 nm, giving a layered structure material consisting mainly of platelike particles. The chemical analysis results showed that the structure of [Co(NH(3))(6)](3+) ions was maintained in the interlayer. On the other hand, an H(2)O/NH(3) ligand exchange reaction progressed for the intercalation of [Co(NH(3))(5)Cl](2+) ions, resulting in an increase in the basal spacing from 0.716 to 0.956 nm.     

The stability of the SEI layer, surface composition and the oxidation state of transition metals at the electrolyte-cathode interface impacted by the electrochemical cycling: X-ray photoelectron spectroscopy investigation

The stability of the valence state of the 3d transition metal ions and the stoichiometry of LiMO(2) (M = Co, Ni, Mn) layered oxides at the surface-electrolyte interface plays a crucial role in energy storage applications. The surface oxidation/reduction of the cations caused by the contact of the solids to air or to the electrolyte results in the blocking of the Li-transport through the interface that leads to the fast batteries deterioration. The influence of the end-of-charge voltage on the chemical composition and the oxidation state of 3d transition metal ions, as well as the stability of the solid-electrolyte interface formed during the electrochemical Li-deintercalation/intercalation of the LiCoO(2) and Li(Ni,Mn,Co)O(2), have been investigated by X-ray photoelectron spectroscopy. While the chemical composition of the solid-electrolyte interface is similar for both layered oxide surfaces, the electrochemical cycling to some critical voltage values leads to the disappearance of the interface. By the analysis of the shape of the 2p and 3s photoelectron emissions we show that the formation of the solid-electrolyte interface layer correlates with the partial reduction of the trivalent Co ions at the electrolyte-LiCoO(2) interface and the amount of the Co(2+) ions is increased as the solid-electrolyte interface vanishes. In contrast, the Mn(4+), Co(3+) and Ni(2+) ions of the Li(Ni,Mn,Co)O(2) are stable at the interface under the electrochemical cycling to higher end-of-charge voltage. A correlation between deterioration of the LiCoO(2) and Li(Ni,Mn,Co)O(2) batteries and the change of electronic structure at the surface/interface after the electrochemical cycling has been found. The dissolution of the solid-electrolyte interface layer might be the reason for the fast deterioration of the Li-ion batteries.     

Transfer of tetra-n-alkylammonium ions from water to nitrobenzene: Chronopotentiometric determination of kinetic parameters

The transfer from water to nitrobenzene of tetraethylammonium (TEA), tetrapropyl-ammonium (TPA) and tetrabutylammonium (TBA) ions is investigated under galvanostatic conditions. The current density range extends from 10 to 100 μA cm^?2. A treatment similar to that which is already established in the chronopotentiometric study of the metal—solution semi-reversible electrochemical process is applied for the determination of the kinetic parameters of the water—nitrobenzene ion transfer.     

Topotactic Conversion of β‐Helix‐Layered Silicate into AST‐Type Zeolite through Successive Interlayer Modifications

AST‐type zeolite with a plate morphology can be synthesized by topotactic conversion of a layered silicate (β‐helix‐layered silicate; HLS) by using N,N‐dimethylpropionamide (DPA) to control the layer stacking of silicate layers and the subsequent interlayer condensation. Treatment of HLS twice with 1) hydrochloric acid/ethanol and 2) dimethylsulfoxide (DMSO) are needed to remove interlayer hydrated Na ions and tetramethylammonium (TMA) ions in intralayer cup‐like cavities (intracavity TMA ions), both of which are introduced during the preparation of HLS. The utilization of an amide molecule is effective for the control of the stacking sequence of silicate layers. This method could be applicable to various layered silicates that cannot be topotactically converted into three‐dimensional networks by simple interlayer condensation by judicious choice of amide molecules.     

Using a Buffer Gas Modifier to Change Separation Selectivity in Ion Mobility Spectrometry

The mobilities of a set of common α-amino acids, four tetraalkylammonium ions, 2,4-dimethyl pyridine (2,4-lutidine), 2,6-di-tert-butyl pyridine (DTBP), and valinol were determined using electrospray ionization-ion mobility spectrometry-quadrupole mass spectrometry (ESI-IMS-QMS) while introducing 2-butanol into the buffer gas. The mobilities of the test compounds decreased by varying extents with 2-butanol concentration in the mobility spectrometer. When the concentration of 2-butanol increased from 0.0 to 6.8 mmol m(-3) (2.5×10(2) ppmv), percentage reductions in mobilities were: 13.6% (serine), 12.2% (threonine), 10.4% (methionine), 10.3% (tyrosine), 9.8% (valinol), 9.2% (phenylalanine), 7.8% (tryptophan), 5.6% (2,4-lutidine), 2.2% (DTBP), 1.0% (tetramethylammonium ion, TMA, and tetraethylammonium ion, TEA), 0.0% (tetrapropylammonium ion, TPA), and 0.3% (tetrabutylammonium ion, TBA). These variations in mobility depended on the size and steric hindrance on the charge of the ions, and were due to formation of large ion-2-butanol clusters. This selective variation in mobilities was applied to the resolution of a mixture of compounds with similar reduced mobilities such as serine and valinol, which overlapped in N(2)-only buffer gas in the IMS spectrum. The relative insensitivity of tetraalkylammonium ions and DTBP to the introduction of 2-butanol into the buffer gas was explained by steric hindrance of the four alkyl substituents in tetraalkylammonium ions and the two tert-butyl groups in DTBP, which shielded the positive charge of the ion from the attachment of 2-butanol molecules. Low buffer gas temperatures (100 °C) produced the largest reductions in mobilities by increasing ion-2-butanol interactions and formation of clusters; high temperatures (250 °C) prevented the formation of clusters, and no reduction in ion mobility was obtained with the introduction of 2-butanol into the buffer gas. Low temperatures and high concentrations of 2-butanol produced a series of ion clusters with one to three 2-butanol molecules in compounds without steric hindrance. Clusters of two and three molecules of 2-butanol were also visible. Ligand-saturation on the positive ions with 2-butanol molecules occurred at high concentrations of modifier (6.8 mmol m(-3) at 150°C); when saturated, no further reduction in mobility occurred when 2-butanol was introduced into the buffer gas.     

2D层状焦磷酸锰髤[NH_4]_2[Mn_3(P_2O_7)_2(H_2O)_2]的结构和磁性研究

由于具有开放骨架的金属磷酸盐在催化、吸附、主客体组装以及光学、磁学等方面的应用[1~3],因此合成具有开放骨架的金属磷酸盐一直吸引着人们的广泛关注。自从1982年美国联合碳化公司(U.C.C.)开发出系列磷酸铝分子筛AlPO4鄄n[4]以来,大量具有开放骨架的金属磷酸盐(金属=Ga,In,F     

The P2-Na(2/3)Co(2/3)Mn(1/3)O2 phase: structure, physical properties and electrochemical behavior as positive electrode in sodium battery

Manganese substituted sodium cobaltate, Na(2/3)Co(2/3)Mn(1/3)O(2), with a layered hexagonal structure (P2-type) was obtained by a co-precipitation method followed by a heat treatment at 950 °C. Powder X-ray diffraction analysis revealed that the phase is pure in the absence of long-range ordering of Co and Mn ions in the slab or Na(+) and vacancy in the interslab space. The oxidation states of the transition metal ions were studied by magnetic susceptibility measurements, electron paramagnetic resonance (ESR) and (23)Na magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The charge compensation is achieved by the stabilization of low-spin Co(3+) and Mn(4+) ions. The capability of Na(2/3)Co(2/3)Mn(1/3)O(2) to intercalate and deintercalate Na(+) reversibly was tested in electrochemical sodium cells. It appears that the P2 structure is maintained during cycling, the cell parameter evolution versus the sodium amount is given. From the features of the cycling curve the formation of an ordered phase for the Na(0.5)Co(2/3)Mn(1/3)O(2) composition is expected.     

Intercalation of poly(oxyethylene) alkyl ether into a layered silicate kanemite

Poly(oxyethylene) alkyl ether (CnEOm) is intercalated into the interlayer space of a layered silicate kanemite by using layered hexadecyltrimethylammonium (C16TMA) intercalated kanemite (C16TMA-kanemite) as the intermediate. C16TMA-kanemite was treated with an aqueous solution of C16EO10, and the intercalation of C16EO10 was confirmed by the slight increase in the basal spacing (from 2.92 to 3.34 nm) with the increase in the carbon content, yielding C16EO10-C16TMA-kanemite. The product was dispersed again in a C16EO10 aqueous solution, and then 1.0 M HCl was added to the suspension to remove C16TMA ions completely. The basal spacing was further increased (from 3.34 to 5.52 nm) and the content of nitrogen was virtually zero, indicating further intercalation of C16EO10 molecules and complete elimination of C16TMA ions simultaneously. Though C16EO10 molecules are not directly intercalated into kanemite, the mutual interactions among C16TMA ions, C16EO10 molecules, and the interlayer silicate surfaces effectively induce the intercalation of C16EO10. C16EO10-kanemite shows a reversible adsorption of n-decane and water owing to the hydrophobicity and hydrophilicity of C16EO10, respectively, in the interlayer space. Layered CnEO10-kanemites (n = 12 and 18) were also synthesized in a manner similar to layered C16EO10-kanemite.     

Redox properties of manganese-containing zirconia solid solution catalysts analyzed by in situ UV-vis spectroscopy and crystal field theory

The optical absorption spectra of manganese-promoted sulfated zirconia, a highly active alkane isomerization catalyst, were found to be characterized by oxygen-to-manganese charge-transfer transitions at 300-320 nm and d-d transitions of manganese ions at 580 and 680 nm. The latter were attributed to Mn(4+) and Mn(3+) ions, which are known to be incorporated in the zirconia lattice. The oxygen surroundings of these ions were modeled assuming a substitutional solid solution. The crystal field splittings, vibronic coupling constants, and oscillator strengths of the manganese ions were calculated on the basis of a cluster model that considers the manganese center as a complex with the adjacent ions of the lattice as ligands. The ratio of Mn(3+) to Mn(4+) ions was determined using the spectra and the model, and the relative concentrations of Mn(2+), Mn(3+), and Mn(4+) ions were determined with the help of the average valence known from X-ray absorption data in the literature. The redox behavior of manganese-promoted sulfated zirconia in oxidizing and inert atmosphere was elucidated at temperatures ranging from 323 to 773 K.     

单斜层状结构锂离子电池正极材料LiY_xMn_(1-x)O_2的合成及其电化学性能

以Na2CO3、(CH3CO2)2Mn.4H2O、Y2O3和CH3COOLi.2H2O为原料,采用高温固相法经过2次灼烧和水热离子交换法得到一系列钇掺杂的LiMn1-xYxO2(x:0.01,0.02,0.03,0.05)化合物。通过XRD、XPS、循环伏安及恒电流充放电测试技术,研究了钇掺杂离子对合成正极材料结构及电化学性能的影响。结果表明,所得产物均具有单斜层状结构。合适的钇掺杂可以起到扩展锂离子脱嵌通道和稳定骨架结构的作用,钇离子的引入部分取代原有的三价锰离子,由于钇离子的离子半径较三价锰离子大,因此稀土掺杂锰酸锂材料的晶胞参数比未掺杂材料大,在一定程度上扩充了锂离子迁移的三维通道,更有利于锂离子的嵌入与脱嵌,提高单斜层状LiMnO2材料的电化学循环可逆性及循环稳定性。通过对所得化合物进行了钇掺杂量及电化学性能的研究,得到性能比较优良的LiY0.021Mn0.979O2化合物,其首次放电比容量为125.7mA.h/g,100次循环以后,放电比容量达212.1mA.h/g,远高于未掺杂材料的放电容量138mA.h/g。交流阻抗测试结果表明,Y3+的掺入能降低材料的电化学反应阻抗和提高材料中Li+的扩散能力。     

Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO2 electrocatalysts

Manganese oxides function as efficient electrocatalysts for water oxidation to molecular oxygen in strongly alkaline conditions, but are inefficient at neutral pH. To provide new insight into the mechanism underlying the pH-dependent activity of the electrooxidation reaction, we performed UV-vis spectroelectrochemical detection of the intermediate species for water oxidation by a manganese oxide electrode. Layered manganese oxide nanoparticles, δ-MnO(2) (K(0.17)[Mn(4+)(0.90)Mn(3+)(0.07)□(0.03)]O(2)·0.53H(2)O) deposited on fluorine-doped tin oxide electrodes were shown to catalyze water oxidation at pH from 4 to 13. At this pH range, a sharp rise in absorption at 510 nm was observed with a concomitant increase of anodic current for O(2) evolution. Using pyrophosphate as a probe molecule, the 510 nm absorption was attributable to Mn(3+) on the surface of δ-MnO(2). The onset potential of the water oxidation current was constant at approximately 1.5 V vs SHE from pH 4 to pH 8, but sharply shifted to negative at pH > 8. Strikingly, this behavior was well reproduced by the pH dependence of the onset of 510 nm absorption, indicating that Mn(3+) acts as the precursor of water oxidation. Mn(3+) is unstable at pH < 9 due to the disproportionation reaction resulting in the formation of Mn(2+) and Mn(4+), whereas it is effectively stabilized by the comproportionation of Mn(2+) and Mn(4+) in alkaline conditions. Thus, the low activity of manganese oxides for water oxidation under neutral conditions is most likely due to the inherent instability of Mn(3+), whose accumulation at the surface of catalysts requires the electrochemical oxidation of Mn(2+) at a potential of approximately 1.4 V. This new model suggests that the control of the disproportionation and comproportionation efficiencies of Mn(3+) is essential for the development of Mn catalysts that afford water oxidation with a small overpotential at neutral pH.     

二氧化钛柱撑层状氧化锰微孔材料的合成及表征

Na型层状锰氧化物于0.1 mol/L HCl 溶液中离子交换制得前驱体H型层状锰氧化物. H型层状锰氧化物在十二胺乙醇溶液中反应得到层间距为2.62 nm的中间产物——十二胺插入的层状锰氧化物, 该中间产物在异丙醇钛和乙醇的混合溶液中溶剂热处理得到层间距为1.24 nm的钛酸柱撑层状锰氧化物. 在300 ℃条件下经2 h焙烧得到二氧化钛铸型氧化锰微孔材料. 应用XRD, DSC-TGA, SEM, TEM, IR, 氮气吸附实验及元素分析进行了不同阶段所得试样的分析表征. 结果表明十二胺分子在锰氧层间的最大插入量为2.2 mmol/g, 异丙醇钛分子的置换插入生成了组成为Mn_7.00Ti_1.74O_23.3(C₁₂H₂₅NH₂)_0.52•1.93H₂O的铸型层状锰氧化物. 300 ℃焙烧处理所得二氧化钛铸型氧化锰微孔材料的比表面积为140 m²/g.     

Density and ultrasonic absorption studies of the interaction between polyions and hydrophobic counterions

The volume changes associated with the interaction between tetra-n-propylammonium, propylammonium and butylammonium ions with the polyethylenesulphonate ion (PES) have been determined from density measurements. The excess ultrasonic absorption of solutions of PES and polystyrenesulphonic (PSS) acids has been measured as a function of the neutralization degree by tetramethylammonium (TMA) and tetra-n-butylammonium (TBA) hydroxides. The results confirm that a negligible volume change is associated with the interaction between tetramethylammonium ions and polyions. They indicate that the interaction of large tetraalkylammonium (TAA) ions with polyions gives rise to a small contraction. This effect may be due to [1] disruption of the organisation of the water molecules about the TAA ion alkyl chain when the chains come close enough to polyion charged sites, under the effect of the electrical charges; [2] to enhanced TAA-TAA interactions in the neighbourhood of polyions, owing to the so-called condensation phenomenon; and [3] to hydrophobic interactions between TAA ions and polyions, in the case of hydrophobic polyions such as PSS.     

Mapping the synthesis of low nuclearity polyoxometalates from octamolybdates to Mn-Anderson clusters

A comprehensive study of the isomer-independent synthesis of TRIS ((HOCH(2))(3)CNH(2)) Mn-Anderson compounds from Na(2)MoO(4)·2H(2)O, via the corresponding octamolybdate species, is presented. Three octamolybdate salts of [Mo(8)O(26)](4-) in the β-isomer form, with tetramethylammonium (TMA), tetraethylammonium (TEA) and tetrapropylammonium (TPA) as the counter cation, were synthesised from the sodium molybdate starting material. Fine white powdery products for the three compounds were obtained, which were fully characterised by elemental analysis, TGA, solution and solid state Raman, IR and ESI-MS, revealing a set ratio of Na and organic cations for each of the three compounds; (TMA)(2)Na(2)[Mo(8)O(26)] (1), (TEA)(3)Na(1)[Mo(8)O(26)] (2) and (TPA)(2)Na(2)[Mo(8)O(26)] (3), and the analyses also confirmed that the three compounds all consisted of the octamolybdate in the β-isomeric form. ESI-MS analyses of 1, 2 and 3 show similar fragmentation for these β-isomers compared to the previously reported study for the α-isomer ((TBA)(4)[α-Mo(8)O(26)]) (A) in the synthesis of ((TBA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)]) (B), and compounds 1, 2 and 3 were successfully used to synthesise equivalent TRIS Mn-Anderson compounds: (TMA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (4), (TEA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (5) and (TPA)(2)Na(1)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (6), as well as Na(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (7). This is the first example where symmetric organically-grafted Mn-Anderson compounds have been synthesised in DMF from anything but the {Mo(8)O(26)} α-isomer.