Second-order Jahn-Teller Research Articles

High-pressure synthesis, structure, phase relation of polar LiNbO3-type ZnTiO3

Ferroelectricity, piezoelectricity, pyroelectricity, and second-order nonlinear optical behavior are technologically important. Because these properties are attributable to the noncentrosymmetric (NCS) structure[1], the search for materials exhibiting such characteristics must begin with a search of NCS materials. Among them, LiNbO3-type (LN-type) compounds with a chemical formula of ABX3 exhibit NSC structures with hexagonal polar space group R3c whose BX6 octahedra three-dimensionally share their corners the same as perovskite-type compounds[2]. In LN-type compounds, the A cation - B cation repulsion directs the spontaneous polarization along c-axis(Fig. 1). Therefore, we might find attractive functional properties by the selection of constituent ions based on their having a naturally occurring polar LN-type structure attributable to the cation-cation repulsion. With the ideas mentioned above, we have investigated the high-pressure synthesis and characterization of novel LN-type oxides such as ZnSnO3, PbNiO3, CdPbO3 as well as known MnMO3 (M = Ti, Sn). Recently, we have successfully synthesized a polar LN-type titanate ZnTiO3 (LN-ZTO) under high pressure and high temperature [3]. The first principles calculation indicates that LN-ZTO is a meta-stable phase obtained by the transformation in the decompression process from the perovskite-type phase, which is stable at high pressure and high temperature. The Rietveld structural refinement reveals that LN-ZTO exhibits greater intra-distortion of the TiO6 in LN-ZTO than that of the SnO6 in LN-type ZnSnO3 (LN-ZSO). The estimated spontaneous polarization are greater than those of LN-ZSO, which is attributed to the great displacement of Ti along c-axis and the greater Born effective charge of Ti (+6.1) than that of Sn (+4.1). Furthermore, the spontaneous polarization of LN-ZTO is greater than that of LiNbO3, indicating that LN-ZTO, like LiNbO3, is a candidate ferroelectric material with high performance. The second harmonic generation (SHG) response of LN-ZTO is 24 times greater than that of LN-ZSO. The findings indicate that the intra-octahedral distortion, spontaneous polarization, and SHG response are caused by the stabilization of the polar LN-type structure and reinforced by the second-order Jahn-Teller effect attributable to the orbital interaction between oxygen ions and d0 ions such as Ti4+. We also discuss the relationship between the intra-distortion of BO6 and polarity in several LN-type oxides.

Strong second harmonic generation (SHG) originating from combined second-order Jahn-Teller (SOJT) distortive cations in a new noncentrosymmetric tellurite, InNb(TeO4)2.

Pure polycrystalline bulk samples and single crystals of a novel polar noncentrosymmetric (NCS) indium niobium tellurium oxide, InNb(TeO4)2, have been synthesized through solid-state reactions with In2O3, Nb2O5, and TeO2. InNb(TeO4)2 exhibits a three-dimensional structural backbone consisting of layers of corner-shared InO6 octahedra, layers of corner-shared NbO6 octahedra, and chains of corner-shared TeO4 polyhedra. The infrared spectrum shows In-O, Nb-O, and Te-O vibrations, and the UV-vis diffuse reflectance spectrum shows a band gap of 3.5 eV for the reported material. Thermal analysis indicates that InNb(TeO4)2 is thermally stable to 740 °C. Powder second-order nonlinear optical (NLO) measurements reveal that InNb(TeO4)2 has a strong second harmonic generation (SHG) efficiency, 100 times that of α-SiO2. A detailed structural examination indicates that the strong SHG is due to the combined net polarization originating from the distorted environment of second-order Jahn-Teller (SOJT) cations such as Nb(5+) and Te(4+). Elemental analysis, the magnitude of distortion, and calculations of dipole moments for InNb(TeO4)2 are also presented.

Pure and Zn-doped Pt clusters go flat and upright on MgO(100).

Pure and doped sub-nanoclusters can exhibit superb catalytic activity, which, however, strongly depends on their size, shape, composition, and the nature of the support. This work is about surface-deposited sub-nano Pt-based clusters, which are promising catalysts for the reactions of dehydrogenation. Using density functional theory and ab initio calculations, and an ab initio genetic algorithm for finding the global minima of clusters, we found a peculiar effect that Pt5 and Pt4Zn clusters exhibit upon deposition on MgO(100). Both of them change shapes from the gas phase 3-D form to a planar form, and they stand upright on the support. Several reasons are responsible for this behaviour. In part, clusters go flat due to the electron transfer from the support. Indeed, the anionic Pt5(-) and Pt4Zn(-) species are flat also in the gas phase. Charging induces the second-order Jahn-Teller effect (or partial covalency) facilitated by the recruitment of the higher-energy 6p atomic orbitals on Pt into the valence manifold, and that is the reason for the planarization of the anions. Secondly, clusters maximize interactions with the surface O atoms (resulting in further favouring of 2-D structures over 3-D), and avoid contacts with surface Mg atoms (resulting in upright morphologies).

High-Pressure Synthesis, Crystal Structure, and Phase Stability Relations of a LiNbO3-Type Polar Titanate ZnTiO3and Its Reinforced Polarity by the Second-Order Jahn–Teller Effect

A polar LiNbO3-type (LN-type) titanate ZnTiO3 has been successfully synthesized using ilmenite-type (IL-type) ZnTiO3 under high pressure and high temperature. The first principles calculation indicates that LN-type ZnTiO3 is a metastable phase obtained by the transformation in the decompression process from the perovskite-type phase, which is stable at high pressure and high temperature. The Rietveld structural refinement using synchrotron powder X-ray diffraction data reveals that LN-type ZnTiO3 crystallizes into a hexagonal structure with a polar space group R3c and exhibits greater intradistortion of the TiO6 octahedron in LN-type ZnTiO3 than that of the SnO6 octahedron in LN-type ZnSnO3. The estimated spontaneous polarization (75 μC/cm(2), 88 μC/cm(2)) using the nominal charge and the Born effective charge (BEC) derived from density functional perturbation theory, respectively, are greater than those of ZnSnO3 (59 μC/cm(2), 65 μC/cm(2)), which is strongly attributed to the great displacement of Ti from the centrosymmetric position along the c-axis and the fact that the BEC of Ti (+6.1) is greater than that of Sn (+4.1). Furthermore, the spontaneous polarization of LN-type ZnTiO3 is greater than that of LiNbO3 (62 μC/cm(2), 76 μC/cm(2)), indicating that LN-type ZnTiO3, like LiNbO3, is a candidate ferroelectric material with high performance. The second harmonic generation (SHG) response of LN-type ZnTiO3 is 24 times greater than that of LN-type ZnSnO3. The findings indicate that the intraoctahedral distortion, spontaneous polarization, and the accompanying SHG response are caused by the stabilization of the polar LiNbO3-type structure and reinforced by the second-order Jahn-Teller effect attributable to the orbital interaction between oxygen ions and d(0) ions such as Ti(4+).

Ferroelectric glycine silver nitrate: a single-crystal neutron diffraction study

Protonated crystals of glycine silver nitrate (C4H10Ag2N4O10) undergo a displacive kind of structural phase transition to a ferroelectric phase at 218 K. Glycine silver nitrate (GSN) is a light-sensitive crystal. Single-crystal X-ray diffraction investigations are difficult to perform on these crystals due to the problem of crystal deterioration on prolonged exposure to X-rays. To circumvent this problem, single-crystal neutron diffraction investigations were performed. We report here the crystal structure of GSN in a ferroelectric phase. The final R value for the refined structure at 150 K is 0.059. A comparison of the low-temperature structure with the room-temperature structure throws some light on the mechanism of the structural phase change in this crystal. We have attempted to explain the structural transition in GSN within the framework of the vibronic theory of ferroelectricity, suggesting that the second-order Jahn-Teller (pseudo-Jahn-Teller) behavior of the Ag(+) ion in GSN leads to structural distortion at low temperature (218 K).

Y2MoSe3O12 and Y2MoTe3O12: Solid-state synthesis, structure determination, and characterization of two new quaternary mixed metal oxides containing asymmetric coordination environment

Two new quaternary yttrium molybdenum selenium/tellurium oxides, Y2MoSe3O12 and Y2MoTe3O12 have been prepared by standard solid-state reactions using Y2O3, MoO3, and SeO2 (or TeO2) as reagents. Single-crystal X-ray diffraction was used to determine the crystal structures of the reported materials. Although both of the materials contain second-order Jahn–Teller (SOJT) distortive cations and are stoichiometrically similar, they reveal different structural features: while Y2MoSe3O12 shows a three-dimensional framework consisting of YO8, MoO6, and SeO3 groups, Y2MoTe3O12 exhibits a layered structure composed of YO8, MoO4, TeO3, and TeO4 polyhedra. With the Mo6+ cations in Y2MoSe3O12, a C3-type intraoctahedral distortion toward a face is observed, in which the direction of the out-of-center distortion for Mo6+ is away from the oxide ligand linked to a Se4+ cation. The Se4+ and Te4+ cations in both materials are in asymmetric coordination environment attributed to the lone pairs. Elemental analyses, infrared spectroscopy, thermal analyses, intraoctahedral distortions, and dipole moment calculations for the compounds are also presented.

α-ScVSe2O8, β-ScVSe2O8, and ScVTe2O8: New Quaternary Mixed Metal Oxides Composed of Only Second-Order Jahn–Teller Distortive Cations

Three new quaternary scandium vanadium selenium/tellurium oxides, α-ScVSe2O8, β-ScVSe2O8, and ScVTe2O8 have been synthesized through hydrothermal and standard solid-state reactions. Although all three reported materials are stoichiometrically similar, they exhibit different crystal structures: α-ScVSe2O8 has a three-dimensional framework structure consisting of ScO6, VO6, and SeO3 groups. β-ScVSe2O8 reveals another three-dimensional framework composed of ScO7, VO5, and SeO3 polyhedra. ScVTe2O8 shows a layered structure with ScO6, VO4, and TeO4 polyhedra. Interestingly, the constituent cations, that is, Sc(3+), V(5+), Se(4+), and Te(4+) are all in a distorted coordination environment attributable to second-order Jahn-Teller (SOJT) effects. Complete characterizations including infrared spectroscopy, elemental analyses, thermal analyses, dipole moment calculation, and the magnitudes of out-of-center distortions for the compounds are reported. Transformation reactions suggest that α-ScVSe2O8 may change to β-ScVSe2O8, and then to Sc2(SeO3)3·H2O under hydrothermal conditions.

Electronic structure effects in the vectorial bond-valence model

The vectorial bond-valence model (VBVM) describes the spatial distribution of bonds to each atom in a system in terms of the vector sum of the incident bond valences. It has been applied in the past to cations not subject to electronic structure effects (e.g., lone-pair or Jahn-Teller effects) in which case the expectation is that the vector sum will be approximately zero. Here we analyze 178 simpleoxide crystal structures and show that the vectorial bond-valence sum is a predictable function of the atomic valence (oxidation state) of each atom and the valence of the strongest bond to atoms for which second-order Jahn-Teller and lone-pair effects play a role in determining molecular geometry. Outliers are uniformly metastable or unstable under ambient conditions, suggesting that deviation from ideal vectorial bond-valence sums might be used as a proxy for some aspect of structural potential energy. These results are all strictly in harmony with the VSEPR model of molecular geometry, but may allow for more quantitative prediction.

Structure-Directing Self-Assembly, Structures and Characterization of Four d0-Transition Metal Oxide/Fluoride Compounds Constructed with Imidazole/1-Methylimidazole/1-Vinylimidazole and Copper(II)/Zinc(II)

Four d0 transition metal oxide/fluoride compounds of V(V), Mo(VI), and Ti(IV), with the “2D layer”, “1D zigzag chain”, “1D linear chain”, and “0D cluster” structures, have been hydrothermally synthesized, by the structure-directing self-assembly of Meimi/Viimi/imi ligands, and other transition metal Zn(II)/Cd(II) ions. The structure-directing property of d0 transition metal oxide/fluoride anions is responsible for the tunable syntheses of novel inorganic solids with structural diversities, while the distortion of the d0 transition metal oxide/fluoride polyhedrons, owing to the second-order Jahn–Teller (SOJT) effect, is the key to engineering the structure-directing property.

Quantum chemical DFT study of two types of stable structures of Ni(II) high-spin binuclear carboxylate complexes

Quantum chemical calculations of the electronic structure of [Ni2(μ-O2CCH3)4(O-DMSO)2] complex were performed using the DFT B3LYP method in the 6-31G(d,p) basis. The calculations made it possible to detect the existence of two types of stable structures of Ni(II) high-spin binuclear carboxylate complexes with different terminal ligands, i.e. with a relatively symmetrical metal-carboxylate Ni2(μ-O2CR)4 framework and with its significant distortion caused by the second-order Jahn-Teller effect.

PbMSeO6 (M = Mo and W): New quaternary mixed metal selenites with asymmetric cationic coordination environments

Two new isostructural mixed metal selenites, PbMSeO(6) (M = Mo(6+) or W(6+)), that are only composed of second-order Jahn-Teller (SOJT) distortive cations have been synthesized by standard solid-state reaction techniques using PbO, SeO(2), and MoO(3) (or WO(3)) as reagents. The structures of the reported materials were determined by single-crystal and powder X-ray diffraction. The materials show a three-dimensional framework structure consisting of chains of corner-shared MO(6) octahedra connected by SeO(3) and PbO(8) polyhedra. All of the constituent cations (M(6+), Se(4+), and Pb(2+)) are in distorted environments attributable to second-order Jahn-Teller (SOJT) effects. While the Mo(6+) cations undergo a C(2)-type intraoctahedral distortion toward an edge, the Se(4+) and Pb(2+) cations are in asymmetric coordination environments attributable to their lone pairs. The SeO(3) polyhedra strongly influence the direction of the Mo(6+) intraoctahedral distortion. Infrared spectroscopy, thermogravimetric analysis, the magnitudes of out-of-center distortions, and dipole moment calculations are also presented. Crystal data: PbMoSeO(6), triclinic, space group P-1 (No. 2), with a = 6.8944(6) Å, b = 7.2219(6) Å, c = 10.8294(9) Å, α = 99.751(2)°, β = 99.996(2)°, γ = 90.041(2)°, V = 523.09(8) Å(3), and Z = 2; PbWSeO(6), triclinic, space group P-1 (No. 2), with a = 6.8689(2) Å, b = 7.2398(2) Å, c = 10.9037(3) Å, α = 99.699(4)°, β = 100.348(3)°, γ = 90.139(4)°, V = 525.50(3) Å(3), and Z = 2.

Structures and stabilities of group 17 fluorides EF3 (E = I, At, and element 117) with spin–orbit coupling

In this work, a recently developed CCSD(T) approach with spin-orbit coupling (SOC) as well as density functional theory (DFT) using various exchange-correlation (XC) functionals are employed to investigate structures and stabilities of group 17 fluorides EF(3) (E = I, At, and element 117). These molecules are predicted to have bent T-shaped C(2v) structures according to the second-order Jahn-Teller (SOJT) effects or the valance shell electron pair repulsion (VSEPR) theory. For IF(3) and (117)F(3), our results are consistent with previous SOC-DFT calculations. However, different XC functionals provide different results for AtF(3) and our SOC-CCSD(T) calculations show that both the C(2v) and D(3h) structures are minima on the potential energy surface and the C(2v) structure is the global minimum for AtF(3). The performance of XC functionals on structures and stabilities of IF(3) and AtF(3) is found to depend on the fraction of the Hartree-Fock exchange (HFX) included in the XC functionals and the M06-2X functional with 54% of HFX providing results that agree best with CCSD(T) results. In addition, although both the C(2v) and D(3h) structures are minima for AtF(3), the energy barrier between them is only 8 kJ mol(-1) for the C(2v) structure and 0.05 kJ mol(-1) for the D(3h) structure. This indicates that the D(3h) structure could not possibly be observed experimentally and AtF(3) can convert easily between the three C(2v) structures. The SOJT term is shown to be reduced by electron correlation for IF(3) and AtF(3). On the other hand, although SOC decreases the energy difference between the C(2v) and D(3h) structures and reduces the deviation of the C(2v) structure from the D(3h) structure, it decreases the frequency of the bond bending mode, which may indicate that SOC actually increases the SOJT term. This could be related to mixing of spin-singlet E' states to low-energy spin-triplet states due to SOC.

Crystal structure evolution and local symmetry of perovskite solid solution Ba[(Fe1/2Nb1/2)1−xTix]O3 investigated by Raman spectra

The local crystal structure and phonon modes of Ba[(Fe1/2Nb1/2)1−xTix]O3 solid solutions (x = 0, 0.2, 0.4, 0.6, 0.8, 0.85, 0.9, 0.95) were investigated by Raman spectroscopy in the range of 100–1000 cm− 1 at room temperature. Typical tetragonal structure with C4v symmetry was determined for Ba[(Fe1/2Nb1/2)0.05Ti0.95]O3, which was in accordance with the X-ray diffraction (XRD) result. Similar Raman spectra with broader peaks were observed for x decreasing from 0.95 to 0.80, indicating weakening of the Ti4 + displacement. New features in low-, medium- and high-wavenumber regions were observed in Raman spectra of Ba[(Fe1/2Nb1/2)1−xTix]O3 system with x ≤ 0.6, which could be attributed to the heterogeneous distribution of multiple B-site ions. Most interestingly, two-mode-like behavior was observed in the high-wavenumber region in Raman spectra of Ba(Fe1/2Nb1/2)O3 and Ba[(Fe1/2Nb1/2)0.8Ti0.2]O3, which was probably caused by very local chemically heterogeneous zones of NbO6 and FeO6. As the existence of the local Nb rich region, slight distortion of octahedron could be expected due to the second-order Jahn-Teller (SOJT) effect of Nb5 + ion. The local composition fluctuation could play an important role in the unique relaxor-like dielectric characteristics of Ba(Fe1/2Nb1/2)O3.

Polymorphism of BaTeMo2O9: A New Polar Polymorph and the Phase Transformation

A new polar polymorph of BaTeMo2O9, α-BaTeMo2O9, has been synthesized by spontaneous crystallization with molten flux based on the TeO2–MoO3 solvent. The two polymorphous phases of BaTeMo2O9 are referred to as β- and α-BaTeMo2O9 according to their crystallization temperature from high to low. The structure of α-BaTeMo2O9 contains two-dimensional (Te2Mo4O18)4– anionic layers interleaved with Ba2+ cations. Each anionic layer is composed of Mo4O20 tetramers connected to TeOx (x = 3, 4) polyhedra. The Mo6+ and Te4+ are in asymmetric coordination environments attributable to second-order Jahn–Teller (SOJT) effects. Second-harmonic generation (SHG) measurements using 1064 nm radiation show that α-BaTeMo2O9 is phase-matchable. Polarization measurements indicate that α-BaTeMo2O9 is not ferroelectric, i.e., the polarization is not “switchable”. In addition, the powder X-ray patterns of the BaTeMo2O9 samples obtained from solid-state reactions revealed that BaTeMo2O9 undergoes an irreversible phase transition from β-BaTeMo2O9 to α-BaTeMo2O9 at ∼570 °C. BaMoO4 is found to lower the energy barrier and stimulate the transformation. Furthermore, structural distortions of both polymorphs were calculated to gain a better understanding of the structure–property relationships. Crystal data: α-BaTeMo2O9, orthorhombic, space group Pca21 (No. 29), a = 14.8683(2) Å, b = 5.6636(1) Å, c = 17.6849(3) Å, V = 1489.21(4) Å3, and Z = 8.

ChemInform Abstract: Hydrated Metal Ions in Aqueous Solution: How Regular Are Their Structures?

AbstractReview: 106 refs.

Synthesis, Structure, and Theoretical Investigations of an Alkaline Earth Vanadate Oxide Compound (Ca4V4O14): Electronic, Optical, and Chemical Bond Properties

One novel purely inorganic d0 polyoxovanadate compound Ca4V4O14 (1) was obtained and characterized structurally. The chain-like [V4O14]8– anion, built up from distorted VO5 trigonal bipyramids and VO4 tetrahedras is rarely observed. The reason for structural distortions is ascribed to the second-order Jahn-Teller effect. The band structure, the density of states, linear optical response functions, the dielectric constants of the static case ϵ(0), and refractive indexes were calculated by the density functional theory method. The nature of the V–O and Ca–O bonds, and of the electronic absorption peak are discussed in detail.

Polar Hexagonal Tungsten Oxide (HTO) Materials: (1) Synthesis, Characterization, Functional Properties, and Structure−Property Relationships in A2(MoO3)3(SeO3) (A = Rb+ and Tl+) and (2) Classification, Structural Distortions, and Second-Harmonic Generating Properties of Known Polar HTOs

Two new polar noncentrosymmetric (NCS) oxides, Rb2(MoO3)3(SeO3) and Tl2(MoO3)3(SeO3), have been synthesized and characterized. The materials exhibit the layered hexagonal tungsten oxide (HTO) structural topology—Class 2, i.e., the MoO6 layers are “capped” on one side by the SeO3 polyhedra. The Rb+ and Tl+ cations are found between the layers. The Mo6+ and Se4+ cations are present in asymmetric coordination environments that are attributable to second-order Jahn−Teller (SOJT) effects. In addition to structural characterization, the materials were characterized by second-harmonic generation (SHG), piezoelectric, and polarization measurements. SHG measurements using 1064-nm radiation revealed doubling efficiencies of 300 and 400 × α-SiO2 for the Rb- and Tl-phases, respectively. Piezoelectric experiments revealed d33 values of ∼9−13 pm/V. Polarization measurements indicate that the materials are not ferroelectric, i.e., the polarization is not “switchable”. The materials are pyroelectric, with total pyroelect...

Ferroelectricity in Perovskites with s0 A-Site Cations: Toward Near-Room-Temperature Multiferroics

materials is based on perovskites, ABO3, with two different cations A and B (for example A 2+ and B 4+ or A 3+ and B 3+ ), in which corner-sharing BO6 octahedra form the three-dimen- sional lattice with every B8 cube containing one A cation. An ideal cubic perovskite, in which the B-OB bonds are linear with A located at the center of each B8 cube (thus forming a AO12 polyhedron), is expected when the tolerance factor t = (rO + rA)/ ffiffiffi 2 p (r O+rB) is unity (rA and rB are the ionic radii of the A and B cations, respectively, with rO as that of the O 2� anion). In most cases, the A cations are small, so that t < 1 and the AO bonds are too long to maintain the ideal cubic structure. Consequently, the A cation moves away from the center of the B8 cube, which is accompanied by the bending of the B-O-B bonds and the rotation of the BO6 octahedra to form a lower-coordinate AOn polyhedron (n < 12) with short AO bonds. The distortion of the ideal cubic perovskite toward a non-centrosymmetric FE structure requires another local instability apart from t < 1, namely, the second-order Jahn-Teller (SOJT) instability (4-6) of the A-site and/or B-site

New Polar Oxides: Synthesis, Characterization, Calculations, and Structure−Property Relationships in RbSe2V3O12 and TlSe2V3O12

Two new polar noncentrosymmetric oxides, RbSe2V3O12 and TlSe2V3O12, have been synthesized and characterized. The oxides are isostructural, as Tl+ exhibits an inert rather than a stereoactive lone pair. The reported materials were structurally characterized by single-crystal X-ray diffraction. The materials exhibit a two-dimensional hexagonal tungsten oxide (HTO) type topology with layers of corner-shared VO6 octahedra. The layers are capped, above and below, by SeO3 polyhedra. The Rb+ and Tl+ cations are found between the layers. The V5+ and Se4+ cations are in asymmetric coordination environments attributable to second-order Jahn−Teller (SOJT) effects. In addition to structural characterization, second-harmonic generation (SHG), piezoelectric, and polarization measurements were performed. SHG measurements using 1064 nm radiation revealed doubling efficiencies ranging from ∼40−50 × α-SiO2. Piezoelectric experiments revealed d33 values of ∼6−12 pm V−1. Polarization measurements indicate the materials are not ferroelectric, i.e., the polarization is not “switchable”. The materials are pyroelectric, with a total pyroelectric coefficient, p, at 45 °C, of −4.4 and −2.6 μC m−2 K−1 for RbSe2V3O12 and TlSe2V3O12, respectively. Thermogravimetric measurements, UV−vis, and infrared spectroscopy were also performed, as were electronic structure calculations. Crystal data: RbSe2V3O12, hexagonal, space group P63 (No. 173), a = b = 7.1364(4) Å, c = 11.4687(13) Å, V = 505.83(7) Å3, and Z = 2; TlSe2V3O12, hexagonal, space group P63 (No. 173), a = b = 7.1248(3) Å, c = 11.4287(11) Å, V = 502.43(6) Å3, and Z = 2.

Synthetic Approaches for Noncentrosymmetric Molybdates

The use of second-order Jahn-Teller active Mo (VI) centers and chiral organic amines is discussed as an approach to crystallographic noncentrosymmetry. Several series of reactions, conducted under mild hydrothermal conditions, were designed to probe important reaction variables. Correlations between reagent and solvent concentrations and the molybdate structure were investigated using composition space analysis, which allows for the isolation of specific reaction variables. The effects of amine structure variation were probed using multiple series of related amines, which consisted of either linear diamines or ethylenediamine derivatives. The addition of fluoride results in the loss of amine-based structural variations. Chiral organic amines were used to demonstrate the viability of using such components to control the three-dimensional symmetry in new materials. The synthesis, structure, and characterization of eight new organically templated polyoxomolybdates and polyoxofluoromolybdates are reported.