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We have developed a family of dinucleating ligands with varying terminal donors to generate dinuclear peroxo and high-valent complexes and to correlate their stabilities and reactivities with their molecular and electronic structures as a function of the terminal donors. It appears that the electron-donating ability of the terminal donors is an important handle for controlling these stabilities and reactivities. Here, we present the synthesis of a new dinucleating ligand with potentially strong donating terminal imidazole donors. As Co II ions are sensitive to variations in donor strength in terms of coordination number, magnetism, UV-Vis-NIR spectra, redox potentials, we probe the electron donation ability of this new ligand in Co II Co II complexes in comparison to the parent Co II Co II complexes with terminal pyridine donors and we synthesize the analogous Co II Co II complexes with terminal 6-methylpyridines and methoxy-substituted pyridines. The molecular structures show indeed strong variations in coordination numbers and bond lengths. These differences in the molecular structures are reflected in the magnetic properties and in the d-d transitions demonstrating that the molecular structures remain intact upon dissolution. The redox potentials are analyzed with respect to the electron donation ability and are the only handle to observe an effect of the methoxy-substituted pyridines. All data taken together show the following order of electron donating ability for the terminal donors: 6-methylpyridines ≪ pyridines < methoxy-substituted pyridines ≪ imidazoles.

Non-heme diiron enzymes activate O 2 for the oxidation of substrates in the form of peroxo FeIII2 or high-valent FeIV2 intermediates. We have developed a dinucleating bis(tetradentate) ligand system that stabilizes peroxo and hydroperoxo FeIII2 complexes with terminal 6-methylpyridine donors, while the peroxo FeIII2 intermediate is reactive with terminal pyridine donors presumably via conversion to a fluent high-valent FeIV2 intermediate. We present here a derivative with electron-donating methoxy substituents at the pyridine donors and its diferric complexes with an {Fe III X(μ-O)Fe III X} (X - = Cl - , OAc - , and OH - ) or an {Fe III (μ-O)(μ-OAc)Fe III } core. The complex-induced oxidation of EtOH with H 2 O 2 provides μ-OAc - , and in acetone, the complex with mixed OH - /OAc - exogenous donors is obtained. Both reactivities indicate a reactive fluent peroxo FeIII2 intermediate. The coupling constant J and the LMCT transitions are insensitive to the nature of the directly bound ligands X - and reflect mainly the electronic structure of the central {Fe III (μ-O)Fe III } core, while Mössbauer spectroscopy and d-d transitions probe the local Fe III sites. The remote methoxy substituents decrease the potential for the oxidation to Fe IV by ∼100 mV, while directly bound OH - in {Fe III (OH)(μ-O)Fe III (OH)} with a short 1.91 Å Fe III -O OH bond decreases the potential by 590 mV compared to {Fe III (OAc)(μ-O)Fe III (OAc)} with a 2.01 Å Fe III -O OAc bond. Interestingly, this Fe III -OH bond is even shorter (1.87 Å) in the mixed OH - /OAc - complex but the potential is the mean value of the potentials of the OH - /OH - and OAc - /OAc - complexes, thus reflecting the electron density of the central {Fe III (μ-O)Fe III } core and not of the local Fe III -OH unit.

A family of dinuclear complexes based on 2,7-disubstituted 1,8-naphthalenediol-ligands has been designed to bind covalently to two neighboring phosphate diester groups in the backbone of DNA. The dinuclear Cu II and Ni II complexes bind to DNA resulting in the inhibition of DNA synthesis in PCR experiments and in a cytotoxicity that is stronger for human cancer cells than for human stem cells of the same proliferation rate. These experiments support but cannot prove that the dinuclear complexes bind as intended to two neighboring phosphate ester groups of the DNA backbone. Here, we evaluate the potential binding mode of the cytotoxic dinuclear Ni II complex using simple phosphate diester models (dimethyl phosphate and diphenyl phosphate). Depending on the reaction conditions, the phosphate diesters bind to the Ni II ions in a bridging or in a terminal coordination mode. The latter occurs by substitution of two coordinated acetates by the phosphate diesters. This reaction has been followed by NMR spectroscopy, which demonstrates that the substitution of acetate by phosphate is thermodynamically strongly favored, while the exchange with excess phosphate is fast on the NMR time scale. The molecular structure of the Ni II complex with two coordinated diphenyl phosphates served as a model for the computational evaluation of the binding to the DNA backbone. This combined experimental and computational study suggests a monodentate coordination mode of the DNA phosphate diesters to the Ni II ions that is assisted by hydrogen bonds with water ligands.

Based on a rational ligand design for stabilizing high-valent {Fe(μ-O)2Fe} cores, a new family of dinucleating bis(tetradentate) ligands with varying terminal donor functions has been developed: redox-inert biomimetic carboxylates in H4julia, pyridines in susan, and phenolates in H4hilde(Me2). Based on a retrosynthetic analysis, the ligands were synthesized and used for the preparation of their diferric complexes [(julia){Fe(OH2)(μ-O)Fe(OH2)}]·6H2O, [(julia){Fe(OH2)(μ-O)Fe(OH2)}]·7H2O, [(julia){Fe(DMSO)(μ-O)Fe(DMSO)}]·3DMSO, [(hilde(Me2)){Fe(μ-O)Fe}]·CH2Cl2, [(hilde(Me2)){FeCl}2]·2CH2Cl2, [(susan){FeCl(μ-O)FeCl}]Cl2·2H2O, [(susan){FeCl(μ-O)FeCl0.75(OCH3)0.25}](ClO4)2·0.5MeOH, and [(susan){FeCl(μ-O)FeCl}](ClO4)2·0.5EtOH, which were characterized by single-crystal X-ray diffraction, FTIR, UV-Vis-NIR, Mössbauer, magnetic, and electrochemical measurements. The strongly electron-donating phenolates afford five-coordination, while the carboxylates and pyridines lead to six-coordination. The analysis of the ligand conformations demonstrates a strong flexibility of the ligand backbone in the complexes. The different hydrogen-bonding in the secondary coordination sphere of [(julia){Fe(OH2)(μ-O)Fe(OH2)}] influences the C-O, C[double bond, length as m-dash]O, and Fe-O bond lengths and is reflected in the FTIR spectra. The physical properties of the central {Fe(μ-O)Fe} core (d-d, μ-oxo → Fe(III) CT, νas(Fe-O-Fe), J) are governed by the differences in terminal ligands - Fe(III) bonds: strongly covalent π-donation with phenolates, less covalent π-donation with carboxylates, and π-acceptation with pyridines. Thus, [(susan){FeCl(μ-O)FeCl}](2+) is oxidized at 1.48 V vs. Fc(+)/Fc, which is shifted to 1.14 V vs. Fc(+)/Fc by methanolate substitution, while [(julia){Fe(OH2)(μ-O)Fe(OH2)}] is oxidized ≤1 V vs. Fc(+)/Fc. [(hilde(Me2)){Fe(μ-O)Fe}] is oxidized at 0.36 V vs. Fc(+)/Fc to a phenoxyl radical. The catalytic oxidation of cyclohexane with TONs up to 39.5 and 27.0 for [(susan){FeCl(μ-O)FeCl}](2+) and [(hilde(Me2)){Fe(μ-O)Fe}], respectively, indicates the potential to form oxidizing intermediates.

The triplesalophen complex [(baron(Me))Co(II)(3)] has been synthesized and characterized. The low-spin Co(II) ions possess an (2)A2 ground state with the magnetic orbitals of dyz type. These are well oriented for a strong π overlap with the bridging phloroglucinol, which results in the strongest ferromagnetic interactions by the spin-polarization mechanism for a 3d phloroglucinol complex.

The chiral triplesalen ligand H6chand(RR) has been used to synthesize the chiral heptanuclear complexes [{(chand(RR))Mn(III)3}2{Fe(II)(CN)6}](ClO4)2 ((RR)[Mn(III)6Fe(II)](ClO4)2) and [{(chand(RR))Fe(III)3}2{Fe(II)(CN)6}](ClO4)2 ((RR)[Fe(III)6Fe(II)](ClO4)2), which have been characterized by single-crystal X-ray diffraction, mass spectrometry, elemental analysis, FT-IR, Mössbauer, and UV-vis spectroscopies, electrochemistry, as well as DC and AC magnetic susceptibility measurements. The half-wave potential of the Fe(III)/Fe(II) couple in (RR)[Mn(III)6Fe(II)](2+) and (RR)[Fe(III)6Fe(II)](2+) is E1/2 = +0.21 and +0.75 V vs. Fc(+)/Fc, respectively, which (i) corresponds to a strong stabilization of the reduced Fe(II) species compared to the redox couple of free [Fe(II/III)(CN)6](4-/3-) and (ii) indicates a significant difference of the electronic coupling with the {(chand(RR))M(t)}(3+) units (M(t) = Mn(III), Fe(III)). Analysis of the DC magnetic data (μeffvs. T, VTVH) of both complexes by a full-matrix diagonalization of the spin-Hamiltonian including isotropic exchange, zero-field splitting with full consideration of the relative orientation of the D tensors and Zeeman interactions reveals ferromagnetic interactions of JMn-Mn = +0.17 ± 0.02 cm(-1) with DMn = -3.4 ± 0.3 cm(-1) for (RR)[Mn(III)6Fe(II)](2+) and JFe-Fe = +0.235 ± 0.005 cm(-1) with DFe = 0 for (RR)[Fe(III)6Fe(II)](2+). The comparison of the molecular structures of (RR)[Mn(III)6Fe(II)](2+) and (RR)[Fe(III)6Fe(II)](2+) with those of the heptanuclear complexes [M(t)6M(c)](n+) using the achiral triplesalen ligand (talen(t-Bu2))(6-) reveals significant differences in the ligand folding, smaller C-C bond distances in the central phloroglucinol ring and larger HOMA values. This indicates more aromatic character and less heteroradialene contribution in (RR)[Mn(III)6Fe(II)](2+) and (RR)[Fe(III)6Fe(II)](2+), which explains the switching from antiferromagnetic coupling in [M(t)6M(c)](n+) to ferromagnetic coupling in (RR)[M(t)6M(c)](n+) by a stronger contribution of the spin-polarization mechanism. This establishes a magnetostructural correlation between the structural parameters describing the aromaticity of the central phloroglucinol unit and the observed exchange couplings JMn-Mn.

A protocol for the synthesis of trinucleating C3-symmetric ligands based on a central meta-phenylene bridging 1,3,5-trimercaptobenzene (thiophloroglucinol) backbone has been established. The key compound turned out to be the trialdehyde obtained from the triple nucleophilic attack of dimethyldithiocarbamate at 1,3,5-tribromo-2,4,6-triformylbenzene. Reacting this trialdehyde with six equivalents of a primary amine results in the simultaneous dithiocarbamate cleavage and Schiff-base formation providing the extended thiophloroglucinol ligands H3bertdien, H6bert(Me), H6bert(t-Bu2), and H6habbi. Reaction with Ni(II) leads to the formation of the trinuclear Ni(II)3 complexes [(bertdien)Ni(II)3](X)3 (X = BPh4(-), BF4(-)), [(bert(Me))Ni(II)3], [(bert(t-Bu2))Ni(II)3], and [(habbi)Ni(II)3], which are characterized spectroscopically, electrochemically, and crystallographically.

A comprehensive synthetic, structural, mass spectrometrical, FT-IR and UV/Vis spectroscopic, electrochemical, and magnetic study on [Mn(III)(6)Mn(III)](3+) (= [{(talen(t-Bu(2)))Mn(III)(3)}(2){Mn(III)(CN)(6)}](3+)) is presented. The high stability of [Mn(III)(6)Mn(III)](3+) in solution allows the preparation of different salts and solvates: [Mn(III)(6)Mn(III)](BPh(4))(3)·3MeOH·3MeCN·3Et(2)O (), [Mn(III)(6)Mn(III)(MeOH)(4)](BPh(4))(3)·5MeOH (), [Mn(III)(6)Mn(III)(MeOH)(6)](BF(4))(3)·9MeOH (), [Mn(III)(6)Mn(III)(MeOH)(6)](PF(6))(2)(OAc)·11MeOH (), and [Mn(III)(6)Mn(III)(MeOH)(6)](lactate)(3)·5MeOH·10H(2)O (). The molecular structure of [Mn(III)(6)Mn(III)](3+) is closely related to the already published [Mn(III)(6)M(c)](3+) complexes (M(c) = Cr(III), Fe(III), Co(III)). ESI mass spectra exhibit the signal of the [{(talen(t-Bu(2)))Mn(III)(3)}(2){Mn(III)(CN)(6)}](3+) trication. FT-IR spectra show the characteristic bands of the triplesalen ligand in [Mn(III)(6)M(c)](3+) and the symmetric ν(C≡N) vibration of the [Mn(III)(CN)(6)](3-) unit at 2135 cm(-1). UV/Vis spectra are dominated by intense transitions of the trinuclear Mn(III)(3) triplesalen subunits above 20,000 cm(-1). The electrochemical studies establish the occurrence of ligand-centered oxidations at ≈1.0 V vs. Fc(+)/Fc, an oxidation of the central Mn(III) at 0.78 V, and a series of reductions of the terminal Mn(III) ions between -0.6 and -1.2 V. AC magnetic measurements indicate single-molecule magnet (SMM) behavior for all compounds. The DC magnetic data are analyzed by a full-matrix diagonalization of the appropriate spin-Hamiltonian including isotropic exchange, zero-field splitting with full consideration of the relative orientation of the D-tensors, and Zeeman interaction, taking into account the diamagnetic nature of the central Mn(III) at low temperatures as inferred from a previous ab initio study. The spin-Hamiltonian simulations indicate Mn(III)-Mn(III) interactions in the -0.37 to -0.70 cm(-1) range within the trinuclear triplesalen subunits and in the -0.02 to +0.23 cm(-1) range across the central Mn(III) ion, while D(Mn) = -3.1 to -5.0 cm(-1). The differences in the exchange parameters and the relaxation behavior of the [Mn(III)(6)Mn(III)](3+) compounds are rationalized in terms of subtle variations in the molecular structures, especially regarding the distortion of the central [Mn(III)(CN)(6)](3-) core and the ligand folding. In comparison with the other [Mn(III)(6)M(c)](3+) compounds, this allows us to establish some general magnetostructural correlations for this class of complexes.

Phase-pure crystalline thin films of a mixed-valence Ru(2)(II,III) metal-organic framework with 1,3,5-benzenetricarboxylate (btc) as a linker were solvothermally grown on amorphous alumina and silica surfaces. Based on the Rietveld refinement, the structure of Ru-MOF was assigned to be analogous to [Cu(3)(btc)(2)] (HKUST-1)., (This journal is © The Royal Society of Chemistry 2011)

The design and first application of a new dinucleating ligand system to mimic high-valent oxidation states of O(2)-dependent diiron enzymes is presented.

Since the discovery that Mn(12)OAc acts as a single-molecule magnet (SMM), an increasing number of transition metal complexes have been demonstrated to behave as SMMs. The signature of a SMM is a slow relaxation of the magnetization at low temperatures accompanied by a magnetic hysteresis. The origin of SMM behaviour is the existence of an appreciable thermal barrier U for spin-reversal called magnetic anisotropy barrier which is related to the combination of a large total spin ground state (S(t)) and an easy-axis magnetic anisotropy. The extensive research on Mn(12)OAc and other SMMs has established more prerequisites for a rational development of new SMMs besides the high-spin ground state and the magnetic anisotropy: the symmetry should be at least C(3) to minimize the quantum tunneling of the magnetization through the anisotropy barrier but lower than cubic to avoid the cancellation of the local anisotropies upon projection onto the spin ground state. Based on these prerequisites, we have designed the ligand triplesalen which combines the phloroglucinol bridging unit for high spin ground states by the spin-polarization mechanism with a salen-like ligand environment for single-site magnetic anisotropies by a strong tetragonal ligand field. The C(3) symmetric, trinuclear complexes of the triplesalen ligand (talen(t-Bu(2)))(6-) exhibit a strong ligand folding resulting in an overall bowl-shaped molecular structure. This ligand folding preorganizes the axial coordination sites of the metal salen subunits for the complementary binding of three facial nitrogen atoms of a hexacyanometallate unit. This leads to a high driving force for the formation of heptanuclear complexes [M(t)(6)M(c)](n+) by the assembly of three molecular building blocks. Attractive van der Waals interactions of the tert-butyl phenyl units of two triplesalen trinuclear building blocks increase the driving force. In this respect, we have been able to synthesize the isostructural series [Mn(III)(6)Cr(III)](3+), [Mn(III)(6)Fe(III)](3+), and [Mn(III)(6)Co(III)](3+) with [Mn(III)(6)Cr(III)](3+) being a SMM. A detailed analysis and comparison of the magnetic properties of the three heptanuclear complexes and the tetranuclear half-unit [Mn(III)(3)Cr(III)](3+) provides significant insight for further optimization of the SMM properties. The modular assembly of the heptanuclear complexes from three molecular building blocks allows the fine-tuning of the molecular and steric properties of each building block without losing the driving force for the formation of the heptanuclear complexes. This possibility of rational improvements of our isostructural series is the main advantage of our supramolecular approach.

The synthesis and characterization of the extended phloroglucinol-ligand H(3)felden based on the trialdehyde 2,4,6-triformylphloroglucinol and its trinuclear Cu(II)(3) complex [(felden){Cu(bpy)}(3)](ClO(4))(3) is presented. This study is motivated to optimize analogous extended phloroglucinol-ligands based on the triketone 2,4,6-triacetylphloroglucinol, which transmit ferromagnetic interactions by the spin-polarization mechanism between three Cu(II) ions and have therefore been applied as the central ligand backbone for a class of heptanuclear single-molecule magnets in a supramolecular approach. A detailed NMR spectroscopic study reveals that the ligand H(3)felden is not in the usually anticipated enol-imine form but in the tautomeric keto-enamine form. The presence of a C(3h) and a C(s) symmetric isomer results in a set of four different signals for each proton. In conjunction with FTIR, electronic absorption spectroscopy, and bond length considerations, it also appears that the complex [(felden){Cu(bpy)}(3)](ClO(4))(3) must be considered as a resonance hybrid of an enolate-imine and a keto-enamine form. A strong contribution of the keto-enamine resonance structure with loss of the central π system explains the weak but ferromagnetic interactions between the Cu(II)S = 1/2 spins. This detailed analysis identifies the strong resonance with unsaturated groups in 2,4,6-position of phloroglucinol as the main source for the low ferromagnetic couplings by the spin-polarization mechanism in these ligands. This provides a synthetic handle to improve the spin-polarization mechanism in these ligands by replacing the imine with amine functions.

The reaction of the tert-butyl-substituted triplesalen ligand H(6)talen(t-Bu(2)) with 2.8 equivalents of Mn(OAc)(2) x 4 H(2)O in MeOH in the presence of NaBPh(4) results in the formation of the one-dimensional (1D) coordination polymer {[{(talen(t-Bu(2)))Mn(3)(MeOH)}(2)(mu(2)-OAc)(3)](mu(2)-OAc)}(n)(BPh(4))(2n) ({[Mn(III)(6)](OAc)}(n)(BPh(4))(2n)) which has been characterized by FTIR, elemental analysis, ESI-MS, single-crystal X-ray diffraction and magnetic measurements. The triplesalen ligand (talen(t-Bu(2)))(6-) provides three salen-like coordination compartments bridged in a meta-phenylene arrangement by a phloroglucinol backbone resulting in the trinuclear Mn(III) base unit {(talen(t-Bu(2)))Mn(3)}(3+). Two of these base units are bridged by three inner acetate ligands giving rise to the hexanuclear complex [{(talen(t-Bu(2)))Mn(3)(MeOH)}(2)(mu(2)-OAc)(3)](3+) ([Mn(III)(6)](3+)). These complexes are bridged by a single external acetate to form a 1D chain as pearls in a pearl necklace. Variable temperature-variable field and mu(eff)vs. T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian consisting of isotropic exchange, zero-field splitting, and Zeeman interaction taking into account the relative orientation of the D-tensors. Satisfactory reproduction of the experimental data have been obtained for parameters sets J(1) = -(0.60 +/- 0.15) cm(-1), J(2) = -(1.05 +/- 0.15) cm(-1), and D(Mn) = -(3.0 +/- 0.7) cm(-1) with J(1) describing the exchange through the phloroglucinol backbone and J(2) describing the exchange through the inner acetates. The non-necessity to incorporate the bridging outer acetates correlates with the longer Mn-O bonds. The experimental data can neither be analyzed without incorporating zero-field splitting nor by the application of a single effective spin ground state.

The deliberate synthesis of the Keplerate [K(20) subset{(W)W(5)O(21)(SO(4))}(12)(VO)(30)(SO(4))(H(2)O)(63)](18-) with 20 pores all closed by K(+) in a supramolecular fashion proves that it is possible to follow new routes in polyoxotungstate chemistry based on pentagonal {(W)W(5)}-type units and to tune magnetic exchange couplings in {(M)M(5)}(12)M'(30) type Keplerates.

Oxidation of the diferric complex [LFe(III)OFe(III)L] to the monoradical complex [LFe(III)OFe(III)L ](+) and the diradical complex [L Fe(III)OFe(III)L ](2+) is followed by a decay into monomeric complexes including a highly reactive putative [LFe(IV)[double bond, length as m-dash]O] complex.

The extension of Robson-type ligands from dinucleating based on 2,6-diformylphenol to trinucleating based on 2,7-diformyl-1,8-naphthalenediol is demonstrated by the synthesis, structural and magnetic characterization of the first trinuclear Cu(II) complex using a 1,8-naphthalenediol derived ligand.

The ligating properties of the 24-membered macrocyclic dinucleating hexaazadithiophenolate ligand (L(Me))2- towards the transition metal ions Cr(II), Mn(II), Fe(II), Co(II), Ni(II) and Zn(II) have been examined. It is demonstrated that this ligand forms an isostructural series of bioctahedral [(L(Me))M(II)2(OAc)]+ complexes with Mn(II) (2), Fe(II) (3), Co(II) (4), Ni(II) (5) and Zn(II) (6). The reaction of (L(Me))2- with two equivalents of CrCl2 and NaOAc followed by air-oxidation produced the complex [(L(Me))Cr(III)H2(OAc)]2+ (1), which is the first example for a mononuclear complex of (L(Me))2-. Complexes 2-6 contain a central N3M(II)(mu-SR)2(mu-OAc)M(II)N3 core with an exogenous acetate bridge. The Cr(III) ion in is bonded to three N and two S atoms of (L(Me))2- and an O atom of a monodentate acetate coligand. In 2-6 there is a consistent decrease in the deviations of the bond angles from the ideal octahedral values such that the coordination polyhedra in the dinickel complex 5 are more regular than in the dimanganese compound 2. The temperature dependent magnetic susceptibility measurements reveal the magnetic exchange interactions in the [(L(Me))M(II)2(OAc)]+ cations to be relatively weak. Intramolecular antiferromagnetic exchange interactions are present in the Mn(II)2, Fe(II)2 and Co(II)2 complexes where J = -5.1, -10.6 and approximately -2.0 cm(-1) (H = -2JS1S2). In contrast, in the dinickel complex 5 a ferromagnetic exchange interaction is present with J = +6.4 cm(-1). An explanation for this difference is qualitatively discussed in terms of the bonding differences.

Two hydrogen-bonds from geometrically constrained OH groups to coordinated oxygen donors shift the reduction potential of a Cu(II) complex by +270 mV as compared to the structurally analogous reference complex missing the OH groups.

A facile synthesis of 2-formyl-1,8-naphthalenediol is reported. Its potential as a general precursor for the preparation of unsymmetrical multidentate chelating ligand systems based on 1,8-naphthalenediol is demonstrated by the synthesis of the dinucleating ligand L(4-)(H(4)L=N,N'-bis(2-(1,8-naphthalenediol)methylidene)propylenediamine). Reaction of H(4) L with copper acetate results in the formation of the unsymmetrical dinuclear Cu(II) complex [LCu(2)](3), which has been structurally characterized by single-crystal X-ray diffraction. One Cu(II) ion is coordinated by a N(2)O(2) compartment of L(4-) and the other Cu(II) ion is coordinated by an O(4) compartment of L(4-) while they are bridged by two aryloxide functions of L(4-). A dimerization of two molecules of 3 to a tetranuclear entity 3(2) occurs through formation of weak apical Cu--O interactions. Analysis of the temperature dependent magnetic susceptibility measurements (2--290 K) established a strong intradimer exchange coupling J(12)=-371 cm(-1). This strong superexchange interaction fits nicely in a magneto-structural correlation which has been established for dinuclear bis(phenoxide)-bridged Cu(II) complexes demonstrating the electronic equivalence of the aryloxides of a phenol and 1,8-naphthalenediol.