Functionalization of Dodecaborates by Mild and Efficient Pd-Catalyzed Formation of B-C Bonds with Boronic Acids.

Hybrid organic-inorganic molecules have recently received great interest due to their unique properties, which give access to their implementation in biological and material sciences. Herein, a new synthetic approach for the direct-linkage of the purely inorganic dodecaborate cluster to organic building blocks through B-C bond is established, using boronic acids as functional groups on the organic moiety, reacting under Suzuki-Miyaura coupling conditions with iodo-undecahydridododecaborate. The choices of ligand (DavePhos) and solvent (N-methylpyrrolidone for electron-poor, CD3 CN for electron-rich groups) are essential for the successful coupling. Ultimately, the newly described methodology is found to be functional-group tolerant covering a wide spectrum of substrates including electron-poor arenes.

Organically Functionalized Mixed-Valent Polyoxo-30-molybdate Wheel and Neutral Tetramolybdenum(V) Oxo Cluster.

The first organofunctionalized mixed-valent polyoxo-30-molybdate wheel, [MoVI18MoV12O84{AsO2(CH3)2}18]18- (Mo30), was synthesized in aqueous, mildly acidic conditions, and upon further acidification, the neutral tetramolybdenum(V) oxo cluster [MoV4O8{AsO2(CH3)2}4] (Mo4) was obtained. Single-crystal X-ray diffraction (XRD) revealed that Mo30 comprises 18 MoVI and 12 MoV ions arranged in a cyclic fashion with alternating {MoV2} and {MoVI3} groups, which are capped by 18 dimethylarsinate ligands, resulting in a novel polyoxo-30-molybdate wheel with a central cavity of ∼1.5 nm. On the other hand, Mo4 has a distorted-cubic structure, with the corners of the cube being occupied by alternating MoV ions and oxo ligands. The compounds were characterized in solution by 1H and 13C NMR and UV-vis spectroscopy and in the solid state by X-ray photoelectron spectroscopy and powder XRD. Mo30 represents a novel type of polyanionic cycle with manyfold possibilities regarding host-guest chemistry.

NiII 36 -Containing 54-Tungsto-6-Silicate: Synthesis, Structure, Magnetic and Electrochemical Studies.

The 36-NiII -containing 54-tungsto-6-silicate, [Ni36 (OH)18 (H2 O)36 (SiW9 O34 )6 ]6- (Ni36 ) was synthesized by a simple one-pot reaction of the Ni2 -pivalate complex [Ni2 (µ-OH2 )(O2 CCMe3 )4 (HO2 CCMe3 )4 ] with the trilacunary [SiW9 O34 ]10- polyanion precursor in water and structurally characterized by a multitude of physicochemical techniques including single-crystal XRD, FTIR, TGA, elemental analysis, magnetic and electrochemical studies. Polyanion Ni36 comprises six equivalent {NiII 6 SiW9 } units which are linked by Ni-O-W bridges forming a macrocyclic assembly. Magnetic studies demonstrate that the {Ni6 } building blocks in Ni36 remain magnetically intact while forming a hexagonal ring with antiferromagnetic exchange interactions between adjacent {Ni6 } units. Electrochemical studies indicate that the first reduction is reversible and associated with the WVI/V couple, whereas the second reduction is irreversible attributed to the NiII/0 couple.

Arsenic(III)-Capped 12-Tungsto-2-Arsenates(III) [M2(AsIIIW6O25)2(AsIIIOH)x]n- (M = CrIII, FeIII, ScIII, InIII, TiIV, MnII) and Their Magnetic Properties.

Six arsenic(III)-capped 12-tungsto-2-arsenates(III) of the type [M2(AsIIIW6O25)2(AsIIIOH)x]n- (M = CrIII, 1; FeIII, 2; ScIII, 3; InIII, 4; TiIV, 5; MnII, 6) have been synthesized in aqueous medium by direct reaction of the elements using a one-pot strategy and structurally characterized by FT-IR spectroscopy, single-crystal XRD, and elemental analysis. Polyanions 1-6 are comprised of two octahedrally coordinated guest metal ions M sandwiched between two {AsW6} units, resulting in a structure with C2h point-group symmetry. Polyanions 1-5 contain tri- and tetravalent metal ion guests M (M = CrIII, FeIII, ScIII, InIII, and TiIV, respectively), and they have one {AsIIIOH} group grafted on each {AsW6} unit, whereas the divalent MnII-containing derivative 6 has two such {AsIIIOH} groups grafted on each {AsW6} unit. Magnetic studies on polyanions 3-5 over the temperature range 1.8-295 K and magnetic fields of 0-7 T confirmed that they are diamagnetic. On the other hand, polyanions 1, 2, and 6 are strongly magnetic and follow the Curie-Weiss law above 30 K. The susceptibility plots of 1 and 6 exhibit broad peaks suggesting short-range antiferromagnetic ordering, while the very weak antiferromagnetic ordering of 2 is overshadowed by traces of a paramagnetic impurity. The magnetization data of 1, 2, and 6 at 1.8 K over 0-7 T were analyzed by using the Heisenberg exchange procedure. Small (negative) values of the obtained J values help in understanding the absence of long-range antiferromagnetic ordering.

FeIII 48 -Containing 96-Tungsto-16-Phosphate: Synthesis, Structure, Magnetism and Electrochemistry.

The 48-FeIII -containing 96-tungsto-16-phosphate, [FeIII 48 (OH)76 (H2 O)16 (HP2 W12 O48 )8 ]36- (Fe48 ), has been synthesized and structurally characterized. This polyanion comprises eight equivalent {FeIII 6 P2 W12 } units that are linked in an end-on fashion forming a macrocyclic assembly that contains more iron centers than any other polyoxometalate (POM) known to date. The novel Fe48 was synthesized by a simple one-pot reaction of an {Fe22 } coordination complex with the hexalacunary {P2 W12 } POM precursor in water. The title polyanion was characterized by single-crystal XRD, FTIR, TGA, magnetic and electrochemical studies.

Peroxouranyl-Containing W48 Wheel: Synthesis, Structure, and Detailed Infrared and Raman Spectroscopy Study.

We report on the first example of a peroxouranium-containing {P8W48} wheel, [{(UO2)4(O2)4}2(P8W48O184)]40- (1), which was synthesized by a one-pot reaction of UO2(NO3)2·6H2O with the 48-tungsto-8-phosphate wheel [H7P8W48O184]33- and aqueous hydrogen peroxide in a pH 6 lithium acetate solution at 50 °C. Polyanion 1 comprises two tetrauranyl squares with side-on peroxo bridging ligands in the cavity of the {P8W48} wheel, and was isolated as the hydrated potassium-lithium salt K18Li22[{(UO2)4(O2)4}2(P8W48O184)]·133H2O (KLi-1), which was characterized in the solid state by single-crystal X-ray diffraction, as well as thermogravimetric and elemental analyses. A detailed Fourier transform infrared and Raman spectroscopy study was also performed.

Lanthanide-Containing 22-Tungsto-2-germanates [Ln(GeW11O39)2]13-: Synthesis, Structure, and Magnetic Properties.

We report on the synthesis and structural characterization of two series of lanthanide-containing 22-tungsto-2-germanates. The first series corresponds to a family of polyanions with the formula [Ln(ß2-GeW11O39)2]13- (LnIII = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Gd (6), Dy (7)), and the second series corresponds to a family with the formula [Ln(ß2-GeW11O39)(α-GeW11O39)]13- (LnIII = Ho (8), Er (9), Tm (10)). All compounds were characterized in the solid state by single-crystal and powder XRD, IR, TGA, and SQUID magnetometry. The polyanions were synthesized in aqueous medium by direct reaction of the monolacunary [ß2-GeW11O39]8- POM precursor with the corresponding lanthanide salts. The structure of the polyanions consists of an 8-coordinated lanthanide ion in a square-antiprismatic geometry, which is sandwiched either between two [ß2-GeW11O39]8- units for 1-7 or between a [ß2-GeW11O39]8- and a [α-GeW11O39]8- unit for 8-10. Furthermore, the effect of the central paramagnetic lanthanide ion on the magnetic behavior of the polyanions was investigated, with the erbium-derivative [Er(ß2-GeW11O39)(α-GeW11O39)]13- (9) showing single-molecule magnet (SMM) behavior.

Peroxo-Cerium(IV)-Containing Polyoxometalates: [CeIV6(O2)9(GeW10O37)3]24-, a Recyclable Homogeneous Oxidation Catalyst.

The class of peroxo-cerium-containing polyoxometalates has been discovered via the synthesis of the 9-peroxo-6-cerium(IV)-containing 30-tungsto-3-germanate, [CeIV6(O2)9(GeW10O37)3]24- (1). Polyanion 1 consists of a cyclic [Ce6(O2)9]6+ assembly that is stabilized by three dilacunary [GeW10O37]10- Keggin fragments. The title polyanion 1 is solution-stable, on the basis of 183W nuclear magnetic resonance, and was shown to act as a recyclable homogeneous catalyst for the selective, microwave-activated sulfoxidation of the model substrate methionine to the sulfoxide in the absence and to the sulfone in the presence of hydrogen peroxide. Solution and solid-state Raman as well as solid-state infrared studies of 1 demonstrated the complete loss (and regain) of the nine peroxo groups in situ during the catalytic cycle, suggesting that the peroxo-free {Ce6(GeW10)3} skeleton remains most likely intact during the catalytic cycle. Solid-state X-ray photoelectron spectroscopy measurements showed that peroxo loss is accompanied by reduction of the cerium ions from +4 to +3, which is fully reversible. Density functional theory calculations are in complete agreement with all of these observations and furthermore suggest that the reduction of the six cerium(IV) ions is accompanied by the formation of molecular dioxygen.

9-Cobalt(II)-Containing 27-Tungsto-3-germanate(IV): Synthesis, Structure, Computational Modeling, and Heterogeneous Water Oxidation Catalysis.

The 9-cobalt(II)-containing trimeric, cyclic polyanion [Co9(OH)3(H2O)6(PO4)2(B-α-GeW9O34)3]21- (1) was synthesized in an aqueous phosphate solution at pH 8 and isolated as a hydrated mixed sodium-cesium salt. Polyanion 1 was structurally and compositionally characterized in the solid state by single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, as well as thermogravimetric and elemental analyses. The magnetic and electrochemical properties of 1 were also studied and compared with those of its phosphorus analogue, [Co9(OH)3(H2O)6(HPO4)2(B-α-PW9O34)3]16- (Co9-P). The electrochemical water oxidation activity of the cesium salt of 1 under heterogeneous conditions was also studied and shown to be superior to that of Co9-P. The experimental results were supported by computational studies.

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage.

The gallium(III)-containing heteropolytungstates [Ga4(H2O)10(ß-XW9O33)2](6-) (X = As(III), 1; Sb(III), 2) were synthesized in aqueous acidic medium by reaction of Ga(3+) ions with the trilacunary, lone-pair-containing [XW9O33](9-). Polyanions 1 and 2 are isostructural and crystallized as the hydrated sodium salts Na6[Ga4(H2O)10(ß-AsW9O33)2]·28H2O (Na-1) and Na6[Ga4(H2O)10(ß-SbW9O33)2]·30H2O (Na-2) in the monoclinic space group P21/c, with unit cell parameters a = 16.0218(12) Å, b = 15.2044(10) Å, c = 20.0821(12) Å, and ß = 95.82(0)°, as well as a = 16.0912(5) Å, b = 15.2178(5) Å, c = 20.1047(5) Å, and ß = 96.2(0)°, respectively. The corresponding tellurium(IV) derivative [Ga4(H2O)10(ß-TeW9O33)2](4-) (3) was also prepared, by direct reaction of sodium tungstate, tellurium(IV) oxide, and gallium nitrate. Polyanion 3 crystallized as the mixed rubidium/sodium salt Rb2Na2[Ga4(H2O)10(ß-TeW9O33)2]·28H2O (RbNa-3) in the triclinic space group P1̅ with unit cell parameters a = 12.5629(15) Å, b = 13.2208(18) Å, c = 15.474(2) Å, α = 80.52(1)°, ß = 84.37(1)°, and γ = 65.83(1)°. All polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR, TGA, and elemental analysis, and polyanion 2 was also characterized in solution by (183)W NMR and UV-vis spectroscopy. Polyanion 2 was used as a homogeneous catalyst toward adenosine triphosphate (ATP) and the DNA model substrate 4-nitrophenylphosphate, monitored by (1)H and (31)P NMR spectroscopy. The encapsulated gallium(III) centers in 2 promote the Lewis acidic synergistic activation of the hydrolysis of ATP and DNA model substrates at a higher rate in near-physiological conditions. A strong interaction of 2 with the P-O bond of ATP was evidenced by changes in chemical shift values and line broadening of the (31)P nucleus in ATP upon addition of the polyanion.

Tetra-Antimony(III)-Bridged 18-Tungsto-2-Arsenates(V), [(LSb(III))4(A-α-As(V)W9O34)2](10-) (L = Ph, OH): Turning Bioactivity On and Off by Ligand Substitution.

Two tetra-antimony(III)-bridged, sandwich-type 18-tungsto-2-arsenates(V), [(LSb(III))4(A-α-As(V)W9O34)2](10-) (L = Ph (1), OH (2)), were prepared and fully characterized in the solid state and in solution. Both polyanions are stable in aqueous physiological medium for at least 24 h (at concentrations ≥2.5 × 10(-6) M). Despite the presence of an isostructural tetra-antimony(III) motif in 1 and 2, distinctly different antibacterial activity was observed for both polyanions. The minimum inhibitory concentrations (MIC) of 1 (7.8-62.5 µg/mL) is lower than for any other organoantimony(III)-containing polyoxometalate reported to date.

CrIII-Substituted Heteropoly-16-Tungstates [CrIII2(B-ß-XIVW8O31)2]14- (X = Si, Ge): Magnetic, Biological, and Electrochemical Studies.

The dichromium(III)-containing heteropoly-16-tungstates [CrIII2(B-ß-SiIVW8O31)2]14- (1) and [CrIII2(B-ß-GeIVW8O31)2]14- (2) were prepared via a one-pot reaction of the composing elements in aqueous, basic medium. Polyanions 1 and 2 represent the first examples of CrIII-containing heteropolytungstates comprising the octatungstate unit {XW8O31} (X = Si, Ge). Magnetic studies demonstrated that, in the solid state, the two polyanions exhibit a weak antiferromagnetic interaction between the two CrIII centers with J = -3.5 ± 0.5 cm-1, with no long-range ordering down to 1.8 K. The ground-state spin of polyanions 1 and 2 was thus deduced to be 0, but the detection of a complex set of EPR signals implies that there are thermally accessible excited states containing unpaired spins resulting from the two S = 3/2 CrIII ions. A comprehensive electrochemistry study on 1 and 2 in solution was performed, and biological tests showed that both polyanions display significant antidiabetic and anticancer activities.

Mixed-Valent Mn16-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties.

The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [Mn(III)10Mn(II)6O6(OH)6(PO4)4(A-α-SiW9O34)4](28-) (1) and [Mn(III)4Mn(II)12(OH)12(PO4)4(A-α-SiW9O34)4](28-) (2) have been prepared by reaction of the trilacunary Keggin precursor [A-α-SiW9O34](10-) with either Mn(OOCCH3)3·2H2O (for 1) or MnCl2·4H2O (for 2), in aqueous phosphate solution at pH 9. Polyanions 1 and 2 comprise mixed-valent, cationic {Mn(III)10Mn(II)6O6(OH)6}(24+) and {Mn(III)4Mn(II)12(OH)12}(24+) cores, respectively, encapsulated by four phosphate groups and four {SiW9} units in a tetrahedral fashion. Both polyanions were structurally and compositionally characterized by single-crystal XRD, IR, thermogravimetric analysis, and X-ray absorption spectroscopy. Furthermore, studies were performed probing the magnetic, electrochemical, oxidation catalytic, and Li-ion battery performance of 1 and 2.

Organoantimony(III)-Containing Tungstoarsenates(III): From Controlled Assembly to Biological Activity.

A family of three sandwich-type, phenylantimony(III)-containing tungstoarsenates(III), [(PhSb(III) ){Na(H2 O)}As(III) 2 W19 O67 (H2 O)](11-) (1), [(PhSb(III) )2 As(III) 2 W19 O67 (H2 O)](10-) (2), and [(PhSb(III) )3 (B-α-As(III) W9 O33 )2 ](12-) (3), have been synthesized by one-pot procedures and isolated as hydrated alkali metal salts, Cs3 K3.5 Na4.5 [(PhSb(III) ){Na(H2 O)}As(III) 2 W19 O67 (H2 O)]⋅41H2 O (CsKNa-1), Cs4.5 K5.5 [(PhSb(III) )2 As(III) 2 W19 O67 (H2 O)]⋅35H2 O (CsK-2), and Cs4.5 Na7.5 [(PhSb(III) )3 (B-α-As(III) W9 O33 )2 ]⋅42H2 O (CsNa-3). The number of incorporated {PhSb(III) } units could be selectively tuned from one to three by careful control of the reaction parameters. The three compounds were characterized in the solid state by single-crystal XRD, IR spectroscopy, and thermogravimetric analysis. The aqueous solution stability of sandwich polyanions 1-3 was also studied by multinuclear ((1) H, (13) C, (183) W) NMR spectroscopy. Effective inhibitory activity against six different kinds of bacteria was identified for all three polyanions, for which the activity increased with the number of incorporated {PhSb(III) } groups.

NHC→SiCl4 : an ambivalent carbene-transfer reagent.

The addition of BCl3 to the carbene-transfer reagent NHC→SiCl4 (NHC=1,3-dimethylimidazolidin-2-ylidene) gave the tetra- and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl4 served as a transfer reagent for the NHC ligand. The addition of BF3 ⋅OEt2 , on the other hand, gave NHC→BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C2 F5 )2 SiCl2 was treated with NHC→SiCl4 . In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) were detected with [(C2 F5 )SiCl3 ](-) as counterion. A similar result was already reported for the reaction of NHC→SiCl4 with (C2 F5 )2 SiH2 , which gave [(NHC)2 SiCl2 H][(C2 F5 )SiCl3 ]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C2 F5 )2 Cl2 and NHC→Si(C2 F5 )2 ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron-poor silylenes. Furthermore, the reactivity of NHC→SiCl4 towards phosphines is discussed. The carbene complex NHC→PCl3 shows similar reactivity to NHC→SiCl4 , and may even serve as a carbene-transfer reagent as well.

Ln12 -Containing 60-Tungstogermanates: Synthesis, Structure, Luminescence, and Magnetic Studies.

A new class of hexameric Ln12 -containing 60-tungstogermanates, [Na(H2 O)6 ⊂Eu12 (OH)12 (H2 O)18 Ge2 (GeW10 O38 )6 ](39-) (Eu12 ), [Na(H2 O)6 ⊂Gd12 (OH)6 (H2 O)24 Ge(GeW10 O38 )6 ](37-) (Gd12 ), and [(H2 O)6 ⊂Dy12 (H2 O)24 (GeW10 O38 )6 ](36-) (Dy12 ), comprising six di-Ln-embedded {ß(4,11)-GeW10 } subunits was prepared by reaction of [α-GeW9 O34 ](10-) with Ln(III) ions in weakly acidic (pH 5) aqueous medium. Depending on the size of the Ln(III) ion, the assemblies feature selective capture of two (for Eu12 ), one (for Gd12 ), or zero (for Dy12 ) extra Ge(IV) ions. The selective encapsulation of a cationic sodium hexaaqua complex [Na(H2 O)6 ](+) was observed for Eu12 and Gd12 , whereas Dy12 incorporates a neutral, distorted-octahedral (H2 O)6 cluster. The three compounds were characterized by single-crystal XRD, ESI-MS, photoluminescence, and magnetic studies. Dy12 was shown to be a single-molecule magnet.

Ti2-Containing 18-Tungsto-2-Arsenate(III) Monolacunary Host and the Incorporation of a Phenylantimony(III) Guest.

The novel Ti2-containing, sandwich-type 18-tungsto-2-arsenate(III) [(Ti(IV)O)2(α-As(III)W9O33)2](14-) (1) was successfully synthesized by the reaction of [TiO](2+) species with [α-As(III)W9O33](9-). The monolacunary polyanion 1 is solution-stable, and a further reaction with 1 equiv of phenylantimony(III) dichloride resulted in [C6H5Sb(III)(Ti(IV)O)2(α-As(III)W9O33)2](12-) (2). Both polyanions 1 and 2 were structurally characterized in the solid state and solution. Electrochemical studies were also performed on both polyanions.

Tetradecanuclear Iron(III)-Oxo Nanoclusters Stabilized by Trilacunary Heteropolyanions.

The tetrameric, multi-Fe(III)-containing polyoxotungstates [Fe14O6(OH)13(P2W15O56)4](31-) (1) and [Na2Fe14(OH)12(PO4)4(A-α-XW9O34)4](20-) (X = Si(IV) (2), Ge(IV) (3)) have been successfully synthesized under conventional reaction conditions in aqueous, slightly acidic (1), or basic (2 and 3) media. Polyanions 1-3 were characterized in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and magnetic studies, and in solution by electrochemistry.

Synthesis and Structure of Hexatungstochromate(III), [H3Cr(III)W6O24]6-.

The hexatungstochromate(III) [H(3)Cr(III)W(6)O(24)](6-) (1) was synthesized in aqueous, basic medium by simple reaction of chromium(III) nitrate nonahydrate and sodium tungstate dihydrate in a 1:6 ratio. Polyanion 1 represents the first Anderson-Evans type heteropolytungstate with a trivalent hetero element. The sodium salt of 1 with the formula Na(6)[H(3)Cr(III)W(6)O(24)]·22H(2)O (1a) was fully characterized in the solid state by single crystal XRD, FT-IR spectroscopy, and thermogravimetric analysis.

Synthesis, detailed characterization, and theoretical understanding of mononuclear chromium(III)-containing polyoxotungstates [Cr(III)(HX(V)W7O28)2]¹³â» (X = P, As) with exceptionally large magnetic anisotropy.

Two monochromium(III)-containing heteropolytungstates, [Cr(III)(HP(V)W7O28)2](13-) (1a) and [Cr(III)(HAs(V)W7O28)2](13-) (2a), were prepared via simple, one-pot reactions in aqueous, basic medium, by reaction of the composing elements, and then isolated as hydrated sodium salts, Na13[Cr(III)(HP(V)W7O28)2]·47H2O (1) and Na13[Cr(III)(HAs(V)W7O28)2]·52H2O (2). Polyanions 1a and 2a comprise an octahedrally coordinated Cr(III) ion, sandwiched by two {PW7} or {AsW7} units. Both compounds 1 and 2 were fully characterized in the solid state by single-crystal XRD, IR spectroscopy, thermogravimetric and elemental analyses, magnetic susceptibility, and EPR measurements. Magnetic studies on 1 and 2 demonstrated that both compounds exhibit appreciable deviation from typical paramagnetic behavior, and have a ground state S = 3/2, as expected for a Cr(III) ion, but with an exceptionally large zero-field uniaxial anisotropy parameter (D). EPR measurements on powder and single-crystal samples of 1 and 2 using 9.5, 34.5, and 239.2 GHz frequencies and over 4-295 K temperature fully support the magnetization results and show that D = +2.4 cm(-1), the largest and sign-assigned D-value so far reported for an octahedral Cr(III)-containing, molecular compound. Ligand field analysis of results from CASSCF and NEVPT2-correlated electronic structure calculations on Cr(OH)6(3-) model complexes allowed to unravel the crucial role of the second coordination sphere of Cr(III) for the unusually large magnetic anisotropy reflected by the experimental value of D. The newly developed theoretical modeling, combined with the synthetic procedure for producing such unusual magnetic molecules in a well-defined and essentially magnetically isolated environment, appears to be a versatile new research area.