Assisted Self-Assembly to Target Heterometallic Mn-Nd and Mn-Sm SMMs: Synthesis and Magnetic Characterisation of [Mn7 Ln3 (O)4 (OH)4 (mdea)3 (piv)9 (NO3 )3 ] (Ln=Nd, Sm, Eu, Gd)*.

In an assisted self-assembly approach starting from the [Mn6 O2 (piv)10 (4-Me-py)2 (pivH)2 ] cluster a family of Mn-Ln compounds (Ln=Pr-Yb) was synthesised. The reaction of [Mn6 O2 (piv)10 (4-Me-py)2 (pivH)2 ] (1) with N-methyldiethanolamine (mdeaH2 ) and Ln(NO3 )3 ⋅ 6H2 O in MeCN generally yields two main structure types: for Ln=Tb-Yb a previously reported Mn5 Ln4 motif is obtained, whereas for Ln=Pr-Eu a series of Mn7 Ln3 clusters is obtained. Within this series the GdIII analogue represents a special case because it shows both structural types as well as a third Mn2 Ln2 inverse butterfly motif. Variation in reaction conditions allows access to different structure types across the whole series. This prompts further studies into the reaction mechanism of this cluster assisted self-assembly approach. For the Mn7 Ln3 analogues reported here variable-temperature magnetic susceptibility measurements suggest that antiferromagnetic interactions between the spin carriers are dominant. Compounds incorporating Ln=NdIII (2), SmIII (3) and GdIII (5) display SMM behaviour. The slow relaxation of the magnetisation for these compounds was confirmed by ac measurements above 1.8 K.

Synthetic Approaches to Metallo-Supramolecular CoII Polygons and Potential Use for H2O Oxidation.

Metal-directed self-assembly has been applied to prepare supramolecular coordination polygons which adopt tetrahedral (1) or trigonal disklike topologies (2). In the solid state, 2 assembles into a stable halide-metal-organic material (Hal-MOM-2), which catalyzes H2O oxidation under photo- and electrocatalytic conditions, operating with a maximum TON = 78 and TOF = 1.26 s-1. DFT calculations attribute the activity to a CoIII-oxyl species. This study provides the first account of how CoII imine based supramolecules can be employed as H2O oxidation catalysts.

Multimodeling Approach to Ferromagnetic Spin-Wave Excitations in the High-Spin Cluster Mn18Sr Observed by Inelastic Neutron Scattering.

The magnetism of the mixed-valence high-spin cluster [Mn18SrO8(N3)7Cl(MedhmpH)12(MeCN)6]Cl2 (1) exhibiting intramolecular ferromagnetic interactions was studied using inelastic neutron scattering (INS), and reliable values for the exchange coupling constants were determined based on the quality of simultaneous fits to the INS and magnetic data. The challenge of the huge size of the Hilbert space (3 375 000) and many exchange coupling constants (7 assuming a C3 symmetry) generally encountered in large spin clusters was resolved as follows: (a) The results of the restricted Hilbert space ferromagnetic cluster spin wave theory were compared to the experimental spectroscopic data. The observed INS transitions were thus assigned to spin wave excitations in a bounded ferromagnetic spin cluster and moreover could be visualized in a straightforward way based on this theory. (b) Simultaneously, Quantum Monte Carlo (QMC) calculations of the temperature-dependent magnetic susceptibility with the same parameter set were compared to the experimental data. Application of state-of-the-art QMC algorithms, as available in the open source ALPS package, in ferromagnetic clusters avoids the full Hamiltonian diagonalization without sacrificing calculation accuracy of the magnetic susceptibility down to the lowest temperatures, which was crucial for the successful analysis. The combined fits revealed two exchange-coupling models with equally good overall agreement to the data. Our preferred model was inspired by magnetostructural correlations and is consistent with them. The model involves three different exchange interactions, one describing the interaction between the core MnIII spins Ja = 14.3(1.0) K and two interactions linking the core and the peripheral MnII spins: Jb = 8.3(4) K and J6 = 3.6(4) K. The use of open-source QMC software and our systematic approach to fitting multiple sets of data obtained by different experimental techniques are described in detail and are generally applicable for understanding large ferromagnetically coupled clusters.

Synthesis of new Mn19 analogues and their structural, electrochemical and catalytic properties.

We report the synthesis and structural characterisation of new Mn19 and Mn18M analogues, [MnIII12MnII7(µ4-O)8(µ3-OCH3)2(µ3-Br)6(HLMe)12(MeOH)6]Br2 (2) and [MnIII12MnII6Sr(µ4-O8(µ3-Cl)8(HLMe)12(MeCN)6]Cl2 cluster (3), where H3LMe is 2,6-bis(hydroxymethyl)-p-cresol. The electrochemistry of 2 and 3 has been investigated and their activity as catalysts in the oxidation of benzyl alcohol has been evaluated. Selective oxidation of benzyl alcohol to benzaldehyde by O2 was achieved using 1 mol% of catalyst with conversions of 74% (2) and 60% (3) at 140 °C using TEMPO as a co-catalyst. No partial conversion of benzaldehyde to benzoic acid was observed. The results obtained revealed that different operative parameters - such as catalyst loading, temperature, time, solvent and the presence of molecular oxygen - played an important role in the selective oxidation of benzyl alcohol.

All-round robustness of the Mn19 coordination cluster system: experimental validation of a theoretical prediction.

Experimental and theoretical studies indicate that achieving the maximum possible ground spin state of ST = 83/2 for the mixed-valent Mn19 coordination cluster is insensitive to replacement of its eight µ3-N3 ligands by µ3-Cl, µ3-Br, µ3-OH or µ3-OMe, substantiating that the ferromagnetic interactions are indeed mediated mainly by the internal (µ4-O) ligands. The robustness of the inorganic {Mn(III)12Mn(II)7(µ4-O)8} core is clear from the molecular structure and ESI-MS studies have shown that the structure of the Mn19 aggregate, and also of its Mn18Y analogue, are stable beyond the solid state.

Spins on a curved surface: an Fe(III)14 ferracalixarene.

The synthesis of the high-nuclearity Fe(III)14 coordination cluster [Fe14(µ3-O)6(µ3-OH)4(µ-OH)3Cl11(dea)4(Hdea)3]Cl·H2O·27MeCN (1) is reported (in which deaH2 = diethanolamine). X-ray crystallographic analysis revealed that compound 1 crystallises in the cubic space group Im3 with Z = 24 and 8 independent Fe centres. Unusually for an Fe(III) coordination cluster, the Fe(III) centres in 1 adopt a range of 4, 5 and 6 coordinate geometries. Complex 1 presents a ferracalixarene topology which can be described in terms of a "half tennis ball" structure and binds a chloride anion guest via multiple hydrogen bonds. The curvature in the structure induced by this topology affects the overall spin structure. A ground spin state of S = 7 is proposed using a combination of magnetic susceptibility data and density functional theory (DFT) calculations.

Magnetic interactions mediated by diamagnetic cations in [Mn18M] (M = Sr2+, Y3+, Cd2+, and Lu3+) coordination clusters.

We previously reported how the synthesis of [Mn(III)12Mn(II)7(µ4-O)8(µ3-η(1)-N3)8(HL(1))12(MeCN)6]Cl2·10MeOH·MeCN (1), which has a Mn19 core corresponding to two supertetrahedral {Mn(II)4Mn(III)6} units sharing a common Mn(II) vertex, can be modified such that the central octacoordinate Mn(II) ion can be replaced by metal ions more likely to favor this coordination geometry such as Dy(III) as exemplified in the compound [Mn(III)12Mn(II)6Dy(III)(µ4-O)8(µ3-Cl)6.5(µ3-N3)1.5(HL)12(MeOH)6]Cl3·25MeOH (2). Here, we report a systematic survey of the effects of incorporating various diamagnetic metal ions M(n+) into this central position. We chose diamagnetic ions with electron configurations with fully occupied or completely empty frontier orbitals in order to gauge the effect on the overall magnetic behavior. The syntheses, structures, and magnetic properties of the heterometallic aggregates [Mn(III)12Mn(II)6Sr(II)(µ4-O)8(µ3-η(1)-N3)7.5(µ3-η(1)-Cl)0.5(HL(1))12(MeCN)6]Cl2·15MeOH (3), [Mn(III)12Mn(II)6Y(III)(µ4-O)8(µ3-η(1)-N3)8(HL(1))12(MeCN)6](NO3)3·11MeOH (4), [Mn(III)12Mn(II)6Cd(II)(µ4-O)8(µ3-η(1)-N3)6.8(µ3-η(1)-Cl)1.2(HL(1))12(MeCN)6](CdCl4)0.25Cl1.5·14.5MeOH (5), and [Mn(III)12Mn(II)6Lu(III)(µ4-O)8(µ3-η(1)-N3)6.5(µ3-η(1)-Cl)1.5(HL(2))12(MeCN)6]Cl3·3H2O·7MeOH·MeCN (6) (H3L(1) = 2,6-bis(hydroxymethyl)-4-methylphenol, H3L(2) = 2,6-bis(hydroxymethyl)-4-fluorophenol) are reported. The aggregates were prepared in one-pot self-assembly reactions of H3L(1) (or H3L(2)), MnCl2·4H2O or Mn(NO3)2·4H2O, NaOAc·3H2O or Et3N, and NaN3 in the presence of the appropriate diamagnetic metal salt in MeCN/MeOH mixtures. Compounds 3-6 crystallize isotypically to 1 in the trigonal space group R3 with Z = 3. The effects on the magnetic properties were investigated, paying attention to the presence of any weak coupling mediated by the diamagnetic cations between the two {Mn(II)3Mn(III)6} S = 39/2 subunits. In the Cd(2+) compound 5, the two {Mn(II)3Mn(III)6} units are magnetically isolated. In 3, 4, and 6, the diamagnetic Sr(2+), Y(3+), and Lu(3+) cations mediate weak antiferromagnetic interactions between the two {Mn(II)3Mn(III)6} subunits. DFT calculations show that the inter-{Mn(II)3Mn(III)6} interactions in the Mn18M systems are attributable to the electronic structure of the central diamagnetic cation, with systems containing trivalent central cations showing stronger antiferromagnetic interactions than those with isoelectronic divalent cations.

Self-assembly of a mononuclear [Fe(III)(L)(EtOH)2] complex bearing an n-dodecyl chain on solid highly oriented pyrolytic graphite surfaces.

The synthesis and structures of the N-[(2-hydroxy-3-methyl-5-dodecylphenyl)methyl]-N-(carboxymethyl)glycine disodium salt (HL) ligand and its neutral mononuclear complex [Fe(III) (L)(EtOH)(2)] (1) are reported. Structural and electronic properties of 1 were investigated by using scanning tunneling microscopy (STM) and current imaging tunneling spectroscopy (CITS) techniques. These studies reveal that molecules of 1 form well-ordered self-assemblies when deposited on a highly oriented pyrolytic graphite (HOPG) surface. At low concentrations, single or double chains (i.e., nanowires) of the complex were observed, whereas at high concentration the complex forms crystals and densely packed one-dimensional structures. In STM topographies, the dimensions of assemblies of 1 found on the surface are consistent with dimensions obtained from X-ray crystallography, which indicates the strong similarities between the crystal form and surface assembled states. Double chains are attributed to hydrogen-bonding interactions and the molecules align preferentially along graphite defects. In the CITS image of complex 1 a strong tunneling current contrast at the positions of the metal ions was observed. These data were interpreted and reveal that the bonds coordinating the metal ions are weaker than those of the surrounding ligands; therefore the energy levels next to the Fermi energy of the molecule should be dominated by metal-ion orbitals.

Unusual nitro-coordination of europium(III) and terbium(III) with pyridinyl ligands.

A new ligand family based on picoline, bipyridine and terpyridine containing a nitro moiety has been synthesized and its coordination and sensitization ability for lanthanide ions has been studied. Three new complexes were characterized by X-ray single crystal diffraction and all three show uncommon coordination of the nitro moiety to the lanthanide ion. 5cTb, a terpyridine-nitro derivative with Tb(NO(3))(3), crystallizes in the orthorhombic space group Pbca with a = 15.125(3), b = 13.776(3), c = 18.716(4) Å, and V = 3899.8(13) Å(3) and is isostructural with its Eu(III) analog (5cEu) with cell parameters a = 15.1341(4), b = 13.7070(4), c = 18.8277(5) Å. 6Eu, a tripodal amine with a nitro-derivatized pyridine with Eu(CF(3)SO(3))(3), crystallizes in the triclinic space group P1 with a = 11.067(2), b = 11.633(2), c = 12.772(3) Å, α = 110.94(3), ß = 97.49(3), γ = 91.42(3)° and V = 1518.1(5) Å(3). Finally, ligand 5a, a bipyridine-nitro derivative, crystallizes in the orthorhombic space group P2(1)/n with a = 3.7128(3), b = 11.7806(8), c = 19.9856(14) Å, ß = 92.925(2)° and V = 873.01(11) Å(3). All four ligands show sensitization of Eu(III) and Tb(III) luminescence.

Contribution of spin and anisotropy to single molecule magnet behavior in a family of bell-shaped Mn11Ln2 coordination clusters.

The synthesis, structures, and magnetic properties of a family of isostructural "bell-shaped" heterometallic coordination clusters [Mn(III)(9)Mn(II)(2)La(III)(2)(µ(4)-O)(7)(µ(3)-O)(µ(3)-OH)(2)(piv)(10.8)(O(2)CC(4)H(3)O)(6.2)(NO(3))(2)(OH(2))(1.5)(MeCN)(0.5)]·12CH(3)CN·2H(2)O (1) and [Mn(III)(9)Mn(II)(2)Ln(2)(µ(4)-O)(7)(µ (3)-O)(µ(3)-OH)(2)(piv)(10.6)(O(2)CC(4)H(3)O)(6.4)(NO(3))(2)(OH(2))]·nCH(3)CN·H(2)O (Ln = Pr(III), n = 8 (2); Ln = Nd(III), n = 10 (3); Ln = Eu(III), n = 17 (4); Ln = Gd(III), n = 13 (5); piv = pivalate) are reported. The complexes were obtained from the reaction of [Mn(III)(2)Mn(II)(4)O(2)(piv)(10)(4-Me-py)(2.5)(pivH)(1.5)] and Ln(NO(3))(3)·6H(2)O in the presence of 2-furan-carboxylic acid (C(4)H(3)OCOOH) in CH(3)CN. Compounds 1-5 are isomorphous, crystallizing in the triclinic space group P1 with Z = 2. The Mn(III) and Mn(II) centers together form the shell of the bell, while the two Ln(III) centers can be regarded as the bell's clapper. The magnetic properties of 1-4 reveal dominant antiferromagnetic interactions between the magnetic centers leading to small spin ground states; while those of 5 indicate similar antiferromagnetic interactions between the manganese ions but with unusually strong ferromagnetic interactions between the Gd(III) ions leading to a large overall spin ground state of S = 11-12. While ac and dc magnetic measurements confirmed that Mn(11)Gd(2) (5) is a single-molecule magnet (SMM) showing hysteresis loops at low temperatures, compounds 1-4 do not show any slow relaxation of the magnetization, indicating that the S = 7 spin of the ferromagnetic Gd(2) unit in 5 is a necessary contribution to its SMM behavior.

A family of 3d-4f octa-nuclear [Mn(III)(4)Ln(III)(4)] wheels (Ln = Sm, Gd, Tb, Dy, Ho, Er, and Y): synthesis, structure, and magnetism.

We present the syntheses, crystal structures, and magnetochemical characterizations for a family of isostructural [Mn(4)Ln(4)] compounds (Ln = Sm, Gd, Tb, Dy, Ho, Er, and Y). They were prepared from the reactions of formic acid, propionic acid, N-n-butyl-diethanolamine, manganese perchlorate, and lanthanide nitrates under the addition of triethylamine in MeOH. The compounds possess an intriguing hetero-octanuclear wheel structure with four Mn(III) and four Ln(III) ions alternatively arranged in a saddle-like ring, where formate ions act as key carboxylate bridges. In the lattice, the molecules stack into columns in a quasi-hexagonal arrangement. Direct current (dc) magnetic susceptibility measurements indicated the depopulation of the Stark components at low temperature and/or very weak antiferromagnetic interactions between magnetic centers. The zero-field alternating current (ac) susceptibility studies revealed that the compounds containing Sm, Tb, and Dy showed frequency-dependent out-of-phase signals, indicating they are single-molecule magnets (SMMs). Magnetization versus applied dc field sweeps on a single crystal of the Dy compound down to 40 mK exhibited hysteresis depending on temperatures and field sweeping rates, further confirming that the Dy compound is a SMM. The magnetization dynamics of the Sm and Y compounds investigated under dc fields revealed that the relaxation of the Sm compound is considered to be dominated by the two-phonon (Orbach) process while the Y compound displays a multiple relaxation process.

New heterometallic [Mn(III)(4)Ln(III)(4)] wheels incorporating formate ligands.

Two heteroctanuclear wheel complexes with an eight-membered saddle-like ring of [Mn(III)(4)Ln(III)(4)] (Ln = Dy, Gd), prepared by employing formates as key carboxylate bridges, exhibit antiferromagnetic interactions between Mn(III) and Ln(III) centers, and the wheel containing anisotropic Dy(III) ions shows SMM behaviour.

Family of Mn(III)(2)Ln(2)(mu(4)-O) compounds: syntheses, structures, and magnetic properties.

An isostructural family of tetranuclear aggregates [Mn(III)(2)Ln(2)(O)(Piv)(2)(hep)(4)(NO(3))(4)].MeCN (where Ln = Y(III) (1), Pr(III) (2), Nd(III) (3), Gd(III) (4), Tb(III) (5), Dy(III) (6), Ho(III) (7), and Yb(III) (8)) is reported. They were obtained from the reactions of 2-(2-hydroxyethyl)pyridine (hepH) with a preformed hexanuclear manganese complex, [Mn(6)], and the respective lanthanide salt. The complexes are isomorphous and represent a new heterometallic 3d-4f complex type for this class of ligand. The structural core of 1-8 consists of a distorted Mn(2)Ln(2) tetrahedron with the four metal centers linking through a mu(4)-O(2-) bridging atom. The magnetic properties of all complexes were investigated by variable temperature magnetic susceptibility and magnetization measurements. The magnetic data of all compounds suggest that antiferromagnetic interactions are present between adjacent paramagnetic centers. Complexes 5-7 containing highly anisotropic lanthanide ions (Tb, Dy, and Ho) show slow relaxation of their magnetization.

Structural motifs and topological representation of Mn coordination clusters.

Polynuclear coordination clusters have become of particular interest in recent times as a result of their relevance to bioinorganic chemistry and to the special area of molecule-based magnetic materials where cluster compounds behave as single-molecule magnets (SMMs). In this review we have focused on describing Mn coordination cluster complexes. Adopting our topological approach for the description of coordination clusters we present a means of classifying the structural motifs found in manganese clusters which range in nuclearity from 5 to 84, as well as some representative heterometallic Mn-M (M = K, Na, Ca, Sr, Ln) cluster complexes that have been reported. This sheds new light on the classification of the types of core structure accessible which, in turn, provides a useful means for developing the so-far missing magneto-structural correlation algorithm for these finite 0-D systems (212 references).

Structures and magnetic properties of Mn(III)4Ln(III)4 aggregates with a "square-in-square" topology.

The structures and magnetic properties of a family of new octanuclear heterometallic 3d-4f complexes [Mn(III)(4)Ln(III)(4)(mu(3)-OH)(4)(mu(2),eta(1)-X)(4)(O(2)CBu(t))(8)(t-bdea)(4)]·solv, where X = N(3)(-), Ln = Y (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); X = OCN(-), Ln = Dy (7); X = NO(3)(-), Ln = Gd (8), Tb (9), Dy (10), Ho (11), Er (12); solv = MeCN or toluene, are reported. The metal topology in the aggregates can be described as consisting of a "Ln(4)-square inscribed in a Mn(4)-square". Complexes 1-7 are prepared by the reactions of t-butyldiethanolamine (t-bdeaH(2)) with a preformed hexanuclear manganese pivalate complex [Mn(6)], the respective lanthanide salt and either NaN(3) or NaNCO, while 8-12 are obtained from the direct reaction of Mn(OAc)(2), Ln(NO(3))(3)·xH(2)O and t-butyldiethanolamine. The magnetic properties of all the complexes were investigated using variable temperature magnetic susceptibility and magnetisation measurements. Similar magnetic behaviour was observed for compounds containing the same lanthanide, indicating that changing the bridging ligand X does not have a significant effect on the magnetic behaviour. The Tb(III) and Dy(III) compounds 4, 5, 7, 9 and 10 all show frequency-dependent ac susceptibilities indicative of a slow relaxation of magnetisation and are therefore considered as Single-Molecule Magnets.

Synthesis, magnetic properties, and STM spectroscopy of cobalt(II) Cubanes [Co(II) (4)(Cl)(4)(HL)(4)].

Reaction of cobalt(II) chloride hexahydrate with N-substituted diethanolamines H(2)L(2-4) (3) in the presence of LiH in anhydrous THF leads under anaerobic conditions to the formation of three isostructural tetranuclear cobalt(II) complexes [Co(II) (4)(Cl)(4)(HL(2-4))(4)] (4) with a [Co(4)(mu(3)-O)(4)](4+) cubane core. According to X-ray structural analyses, the complexes 4 a,c crystallize in the tetragonal space group I4(1)/a, whereas for complex 4 b the tetragonal space group P$\bar 4$ was found. In the solid state the orientation of the cubane cores and the formation of a 3D framework were controlled by the ligand substituents of the cobalt(II) cubanes 4. This also allowed detailed magnetic investigations on single crystals. The analysis of the SQUID magnetic susceptibility data for 4 a gave intramolecular ferromagnetic couplings of the cobalt(II) ions (J(1) approximately 20.4 K, J(2) approximately 7.6 K), resulting in an S=6 ground-state multiplet. The anisotropy was found to be of the easy-axis type (D=-1.55 K) with a resulting anisotropy barrier of Delta approximately 55.8 K. Two-dimensional electron-gas (2DEG) Hall magnetization measurements revealed that complex 4 a is a single-molecule magnet and shows hysteretic magnetization characteristics with typical temperature and sweep-rate dependencies below a blocking temperature of about 4.4 K. The hysteresis loops collapse at zero field owing to fast quantum tunneling of the magnetization (QTM). The structural and electronic properties of cobalt(II) cubane 4 a, deposited on a highly oriented pyrolytic graphite (HOPG) surface, were investigated by means of STM and current imaging tunneling spectroscopy (CITS) at RT and standard atmospheric pressure. In CITS measurements the rather large contrast found at the expected locations of the metal centers of the molecules indicated the presence of a strongly localized LUMO.

Magnetic coordination clusters and networks: synthesis and topological description.

With the discovery of the phenomenon of single-molecule magnetism, coordination chemists have turned their attention to synthesizing cluster aggregates of paramagnetic ions. This has led to a plethora of coordination clusters with various topologies and diverse magnetic properties. In this paper, we present ways of describing and understanding such compounds as well as outlining a new approach, which we have recently developed, to describing cluster topology. Our approach is based upon and pays tribute to the huge contribution made to coordination chemistry through the development of the Schläfli symbols for describing architectures. To illustrate the developments that are taking place in modern coordination chemistry, we start with some basic definitions of relevance to what follows. Then we describe approaches to discovering new magnetically interesting 3d/4f clusters, assigning their topological descriptions. Finally, we show how the concepts behind the construction of metal-organic frameworks can be extended to using clusters as nodes in the frameworks to give super metal-organic frameworks.

An undecanuclear Fe(III) single-molecule magnet.

The undecanuclear complex in [Fe(III)(11)(mu(4)-O)(3)(mu(3)-O)(4)(L)(3)(mu-O(2)CCMe(3))(12)]Cl.5MeCN has been synthesized and characterized by single-crystal X-ray crystallography. Mossbauer spectroscopy and bulk susceptibility studies reveal that the complex has an S = (13)/(2) spin ground state and exhibits single-molecule-magnet behavior.

Tridecanuclear [Mn(III)5Ln(III)8] complexes derived from N-(t)butyl-diethanolamine: synthesis, structures, and magnetic properties.

The synthesis, structures and magnetic properties of a family of heterometallic [Mn(III)(5)Ln(III)(8)(mu(3)-OH)(12)(L(2))(4)(piv)(12)(NO(3))(4)(OAc)(4)](-) (Ln = Pr, 2; Nd, 3; Sm, 4; Gd, 5; Tb, 6) aggregates are reported. The complexes were obtained from the direct reaction of N-(t)butyldiethanolamine (H(2)L(2)) with Mn(OAc)(2) x 4 H(2)O and Ln(NO(3))(3) x 6 H(2)O in the presence of pivalic acid (pivH) in MeCN under ambient conditions. Compounds 2-6 are isomorphous and crystallize in the monoclinic space group P2(1)/n with four molecules in the unit cell. The complexes have a centrosymmetric tridecanuclear anionic core consisting of two distorted inner heterometallic [Mn(III)Ln(III)(3)(mu(3)-OH)(4)](8+) cubane subunits sharing a common Mn vertex flanked by four edge-sharing heterometallic [Mn(III)Ln(III)(2)(mu(3)-OH)(4)](5+) defect cubane units. Complexes 2-6 are the first high-nuclearity 3d-4f aggregates reported to date using (t)Bu-deaH(2) as ligand. These compounds show no evidence of slow relaxation behavior above 1.8 K, which appears to be the consequence of the very weak or non-existent magnetic interactions between the Mn(III) and Ln(III) ions resulting from the particular angles at the bridging oxygens.