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Group (IV) metal oxo clusters represent a unique family of molecular species that are increasingly being utilized in applications ranging from catalysis and materials chemistry to electronics, and sensors. These clusters exhibit distinctive structural features, chemical reactivity, and electronic structure. Nevertheless, their full potential has yet to be fully realized due to the lack of deeper understanding regarding their structure and formation mechanisms, inherent traits, and intricacies in their design, which could ultimately enable significant customization of their properties and overall behaviour. Considering the recently observed reignited interest in the chemistry of group IV molecular species, the scope of this article is to bring to the readers the main chemical characteristics of the family of titanium, zirconium, and hafnium-based clusters, their structural features and their potential in future applications.

The combined use of 2-(2-pyridyl)-1,3-propane-diol (pypdH 2 ) and 2-hydroxymethyl-2-(2-pyridyl)-1,3-propane-diol (pyptH 3 ) in Cu 2+ /4f chemistry has afforded a new family of isostructural [Cu 6 M 4 (pypt) 4 (pypdH) 4 (NO 3 ) 8 ] [M = Gd (1), Tb (2), Dy (3), and Y (4)] complexes. These compounds are based on an unprecedented three-layered symmetric [Cu 6 M 4 (μ-OR) 16 ] 8+ structural core, formed from the connection of the metal ions by bridging alkoxide arms of the organic ligands. Direct current magnetic susceptibility studies for complexes 1-3 revealed the presence of dominant ferromagnetic exchange interactions, suggesting the existence of large spin ground state values. Alternating current magnetic studies indicate the presence of slow-magnetic relaxation in 1-3.

The initial use of a tetradentate Schiff base (LH 2 ) derived from the 2 : 1 condensation between 2-hydroxyacetophenone and cyclohexane-1,2-diamine in 4f-metal chemistry is described. The 1 : 2 reaction of Ln(NO 3 ) 3 · x H 2 O (Ln = lanthanoid or yttrium) and LH 2 in MeOH/CH 2 Cl 2 has provided access to isostructural complexes [Ln(NO 3 ) 3 (L'H 2 )(MeOH)] in moderate to good yields. Surprisingly, the products contain the corresponding Schiff base ligand L'H 2 possessing six aliphatic -CH 2 - groups instead of the -CH-(CH 2 ) 4 -CH- unit of the cyclohexane ring, i.e. an unusual ring-opening of the latter has occurred. A mechanism for this Ln III -assisted/promoted LH 2 → L'H 2 transformation has been proposed assuming transient Ln II species and a second LH 2 molecule as the H 2 source for the reduction of the cyclohexane moiety. DFT calculations provide strong evidence for the great thermodynamic stability of the products in comparison with analogous complexes containing the original intact ligand. The structures of the Pr III , Sm III , Gd III , Tb III , and Ho III complexes have been determined by single-crystal X-ray crystallography. The 9-coordinate Ln III centre in the molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the bidentate chelating organic ligand, and one oxygen atom from the coordinated MeOH group. In the overall neutral bis(zwitterionic) L'H 2 ligand, the acidic H atoms are clearly located on the imino nitrogen atoms and this results in the formation of an unusual 16-membered chelating ring. The coordination polyhedra defined by the nine donor atoms around the 4f-metal-ion centres can be best described as distorted, spherical capped square antiprisms. The Eu III , Tb III , and Dy III complexes exhibit Ln III -based luminescence in the visible region, with the coordinated L'H 2 molecule acting as the antenna. Ac magnetometry experiments show that the Dy III member of the family behaves as an SIM at zero field and under external dc fields of 0.1 and 0.2 T without the enhancement of the peaks' maxima, suggesting that QTM is not the relaxation path. The Gd III complex behaves, rather unexpectedly, as a SIM with two different magnetic relaxation paths occurring at very close temperatures; this behaviour is tentatively attributed to a very small axial zero-field splitting ( D ∼ 0.1 cm -1 ), which cannot be detected by magnetization or susceptibility experiments. The prospects of the present, first results in the lanthanoid(III)-LH 2 chemistry are discussed.

The synthesis, crystal structures, Mössbauer spectra and variable temperature dc and ac magnetic susceptibility studies of a new family of trinuclear heterometallic Fe 3+ /Ln 3+ complexes, [Fe 2 Ln(PhCO 2 ) 3 ((py) 2 CO 2 )((py) 2 C(OMe)O) 2 (NO 3 )Cl] (Ln = Gd (1/Gd), Tb (1/Tb), Dy (1/Dy), and Ho (1/Ho)), where (py) 2 CO 2 2- and (py) 2 are the anions of the - -diol and hemiketal derivatives of di-2-pyridyl ketone, are reported. Compounds 1/Ln are based on an asymmetric "V-shaped" [Fe gem -diol and hemiketal derivatives of di-2-pyridyl ketone, are reported. Compounds 1/Ln are based on an asymmetric "V-shaped" [Fe 3+ (μ-OR)Ln(μ-OR) 2 Fe 3+ structural core formed from the connection of the two terminal Fe 6+ structural core formed from the connection of the two terminal Fe 3+ ion either through one or two alkoxide groups originating from the alkoxide-type bridging ligands. Direct current magnetic susceptibility studies reveal the presence of weak antiferromagnetic interactions between the Fe 3+ ions. Alternating current magnetic studies indicate the presence of a slow-magnetic relaxation process in 1/Dy with an energy barrier 3+ ions. Alternating current magnetic studies indicate the presence of a slow-magnetic relaxation process in 1/Dy with an energy barrier U eff s. The electronic, magnetic and relaxation properties of the complexes were further monitored by variable temperature τ 0 > 80 K the spectra from the complexes comprise two quadrupole doublets the hyperfine parameters of which reflect the distinct coordination environment of the two Fe -7 s. The electronic, magnetic and relaxation properties of the complexes were further monitored by variable temperature 57 < 20 K, the Mössbauer spectra for 1/Dy are affected by magnetic relaxation effects. At 1.5 K, the spectrum of 1/Dy comprises well defined magnetic sextets indicating relaxation times slower than the characteristic time of the Mössbauer technique (10 T s) in agreement with the dynamic magnetic measurements. 1/Gd exhibits broad unresolved magnetic sextets at 1.5 K indicating that the spin relaxation time is of the order of the Mössbauer characteristic time at this temperature. For 1/Tb, 1/Ho the Mössbauer spectra exhibit slight broadening even at the lowest available temperature consistent with magnetic relaxation times less than 10 3+ terminal sites. At T < 20 K, the Mössbauer spectra for 1/Dy are affected by magnetic relaxation effects. At 1.5 K, the spectrum of 1/Dy comprises well defined magnetic sextets indicating relaxation times slower than the characteristic time of the Mössbauer technique (10 -7 s) in agreement with the dynamic magnetic measurements. 1/Gd exhibits broad unresolved magnetic sextets at 1.5 K indicating that the spin relaxation time is of the order of the Mössbauer characteristic time at this temperature. For 1/Tb, 1/Ho the Mössbauer spectra exhibit slight broadening even at the lowest available temperature consistent with magnetic relaxation times less than 10 -7 s.

The 1 : 1 : 1 reaction of YbCl 3 ·6H 2 O, K 3 [Co(CN) 6 ] and bpyO 2 in H 2 O has provided access to a complex with formula [YbCo(CN) 6 (bpyO 2 ) 2 (H 2 O) 3 ]·4H 2 O (1) in a very good yield while its structure has been determined by single-crystal X-ray crystallography and characterised based on elemental analyses and IR spectra. Magnetic susceptibility studies showed the complex to be a field induced single molecule magnet, as confirmed by μ-SQUID measurements. CASSCF calculations confirm the existence of a m = 7/2 ground state, with rather large transverse components, responsible for the fast relaxation characteristic of compound 1 at zero DC field, which is reduced upon application of DC fields. Moreover, a combination of luminescence studies along with CASSCF calculation allows the identification of the band structure of the complex, which is ultimately related to its electronic properties. Compound 1 operates as a luminescent thermometer in the 125-300 K range with a maximum relative thermal sensitivity of ≈0.1% K J = 7/2 ground state, with rather large transverse components, responsible for the fast relaxation characteristic of compound 1 at zero DC field, which is reduced upon application of DC fields. Moreover, a combination of luminescence studies along with CASSCF calculation allows the identification of the band structure of the complex, which is ultimately related to its electronic properties. Compound 1 operates as a luminescent thermometer in the 125-300 K range with a maximum relative thermal sensitivity of ≈0.1% K -1 at 180 K.

The hydrolytically stable dioxime ligand (2 Z -6 Z )-piperidine-2,6-dione (H 3 pidiox) acts as a strong chelator mainly with hard metals in high oxidation states, a pre-requisite for potential applications in metal sequestering processes from aqueous solutions. Reaction of ZrCl 4 with H 3 pidiox in methanol gives the mononuclear compound [Zr IV (η 1 ,η 1 ,η 2 -H 2 pidiox- O , N , O ') 2 (OH 2 ) 2 ]Cl 2 ·H 2 O·CH 3 OH (1), while the same reaction mixture in the presence of KOH gave the pentanuclear ZrOC [ZrIV5(μ 2 -OH) 4 (OH 2 ) 4 (μ 2 -η 1 ,η 1 ,η 2 -Hpidiox- O , N , O ') 4 (η 1 ,η 1 ,η 1 -Hpidiox O , N , O ') 4 ]·5KCl·3CH 3 OH·8H 2 O (2). Compound 1 is formed at very acidic pH = 0, and the pentanuclear ZrOC 2 at higher pH values (pH = 2). Compounds 1 and 2 were characterized by single crystal X-ray structure analysis, multi-nuclear NMR spectroscopy and ESI-MS spectrometry. The single crystal X-ray structure analysis of 1 revealed a mononuclear zirconium(IV) compound containing an eight-coordinate zirconium atom bound to two singly deprotonated H 2 pidiox - ligands and two water molecules in a severely distorted bicapped octahedral geometry. The pentanuclear ZrOC 2 constitutes the second example of a Zr 5 cluster to be reported and the first one in which the four zirconium atoms are arranged in a tetrahedral arrangement with the fifth occupying the center of the tetrahedron. 1D and 2D NMR spectroscopies of the acidic CD 3 OD solutions of complex 1 reveal a fast equilibrium between 1 and 2. Addition of KOH into a CH 3 OH solution of 2 results in the controlled fast transformation of 2 to an asymmetric hexanuclear ZrOC 3 as evidenced by the NMR and real-time ESI-MS solution studies. Further addition of KOH to the solution of 3 leads to the ZrOC 4, and on the basis of NMR and ESI-MS data and in comparison with the known hexanuclear titanium(IV)/H 3 pidiox cluster, it is concluded that the cluster 4 should have a hexanuclear structure. Electrospray ionization mass spectrometry (ESI-MS) demonstrated not only the structural stability 1 and 2 in solution, but also revealed the reversible pH driven dis-assembly/re-assembly process between the monomeric 1 and the pentanuclear ZrOC 2.

The 1 : 2 reaction between Dy(O 2 CMe) 3 ·4H 2 O and 1-acetyl-2-napthol (LH) in MeOH has provided access to the complex [Dy 2 L 6 (MeOH)]·MeOH (1·MeOH) in a good yield. The structures of the isomorphous complex 1·MeOH and its doped diamagnetic yttrium analogue [Dy 0.14 Y 1.86 L 6 (MeOH)]·MeOH (Dy@Y2) have been determined by single-crystal X-ray crystallography and characterized based on elemental analyses, IR spectra, and powder X-ray patterns. Combined dc and ac magnetic susceptibility and the magnetization data for 1 suggest that this complex shows slow magnetic relaxation. Under a 0 Oe dc field, a single relaxation mechanism is seen while two magnetization relaxation processes are evident under a 1500 G external magnetic field. The fit to the Arrhenius law has been performed using the 1.8-10 K ac data, affording an effective barrier for the magnetization reversal of 13 K and 7 K under the external dc field. Theoretical studies have been performed using ab initio and density functional methodologies to understand the electronic structure and the magnetic relaxation dynamics resulting from the single Dy III ion as well as from the dinuclear exchange-coupled states. Rich powder EPR spectra at the X-band and Q-band were obtained from Dy@Y2, as well as from the 1·MeOH dimer, while simulation studies revealed the ferromagnetic nature of the interaction between the Dy III ions in accordance with theoretical studies.

Metal organic frameworks (MOFs) have attracted considerable attention in recent years due to their use in a wide range of environmental, industrial and biomedical applications. The employment of benzophenone-4,4'-dicarboxylic acid (bphdcH2) in MOF chemistry provided access to the 3D mixed metal MOFs [CoNa2(bphdc)2(DMF)2]n (NUIG2) and [ZnK2(bphdc)2(DMF)2]n (NUIG3), and the 2D homometallic MOF [Co2(OH)(bphdcH)2(DMF)2(H2O)2]n(OH)·DMF (1·DMF). 1·DMF is based on a dinuclear SBU and consists of interpenetrating networks with an sql topology. Dc magnetic susceptibility studies were carried out in 1·DMF and revealed the presence of weak antiferomagnetic exchange interactions between the metal centres. NUIG2 and NUIG3 are structural analogues of [ZnNa2(bphdc)2(DMF)2]n (NUIG1), which has shown an exceptionally high encapsulation for ibuprophen (Ibu), NO and metal ions. Both NUIG2 and NUIG3 display high metal ion (CoII, NiII, CuII) adsorption capacity, comparable to that of NUIG1, with NUIG2 exhibiting good performance in Ibu uptake (780 mg Ibu per g NUIG2). Monte Carlo simulations were conducted in NUIG1 in order to assess its adsorption capacity for other guest molecules, and revealed that it possesses an outstanding CO2 uptake at ambient pressure, which is larger than that of the previously reported best functioning species (104 vs. 100 cm3 (stp) per cm3). Furthermore, NUIG1 exhibits high selectivity for CO2 over CH4.

The chiral dicobalt(ii) complex [CoII2(μ2-L)2] (1) (H2L = N2,N6-di(quinolin-8-yl)pyridine-2,6-dicarboxamide) and its tert-butyl analogue [CoII2(μ2-LBu)2] (2) were synthesized and structurally characterized. Addition of one equivalent of AgSbF6 to the dichloromethane solution of 1 and 2 resulted in the isolation of the mixed-valent dicobalt(iii,ii) species [CoIIICoII(μ2-L)2]SbF6 (3) and [CoIIICoII(μ2-LBu)2]SbF6 (4). Homovalent 1 and 2 exhibited catalytic activity towards proton reduction in the presence of acetic acid (AcOH) as the substrate. The complexes are stable in solution while their catalytic turnover frequency is estimated at 10 and 34.6 h-1 molcat-1 for 1 and 2, respectively. Calculations reveal one-electron reduction of 1 is ligand-based, preserving the dicobalt(ii) core and activating the ligand toward protonation at the quinoline group. This creates a vacant coordination site that is subsequently protonated to generate the catalytically ubiquitous Co(iii) hydride. The dinuclear structure persists throughout where the distal Co(ii) ion modulates the reactivity of the adjacent metal site by promoting ligand redox activity through spin state switching.

The metalloantibiotic of formula Ph2Sn(CIP)2 (CIPTIN) (HCIP = ciprofloxacin) was synthesized by reacting ciprofloxacin hydrochloride (HCIP·HCl) (an antibiotic in clinical use) with diphenyltin dichloride (Ph2SnCl2DPTD). The complex was characterized in the solid state by melting point, FT-IR, X-ray Powder Diffraction (XRPD) analysis, 119Sn Mössbauer spectroscopy, X-ray Fluorescence (XRF) spectroscopy, and Thermogravimetry/Differential Thermal Analysis (TG-DTA) and in solution by UV-Vis, 1H NMR spectroscopic techniques and Electrospray Ionisation Mass Spectrometry (ESI-MS). The crystal structure of CIPTIN and its processor HCIP was also determined by X-ray crystallography. The antibacterial activity of CIPTIN, HCIP·HCl, HCIP and DPTD was evaluated against the bacterial species Pseudomonas aeruginosa (P. aeruginosa), Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Staphylococcus epidermidis (S. epidermidis), by the means of Minimum Inhibitory Concentration (MIC), Minimum Bactericidal Concentration (MBC) and Inhibition Zones (IZs). CIPTIN shows lower MIC values than those of HCIP·HCl (up to 4.2-fold), HCIP (up to 2.7-fold) or DPTD (>135-fold), towards the tested microbes. CIPTIN is classified into bactericidal agents according to MBC/MIC values. The developing IZs are 40.8 ± 1.5, 34.0 ± 0.8, 36.0 ± 1.1 and 42.7 ± 0.8 mm, respectively which classify the microbes P. aeruginosa, E. coli, S. aureus and S. epidermidis to susceptible ones to CIPTIN. These IZs are greater than the corresponding ones of HCIP·HCl by 1.1 to 1.5-fold against both the tested Gram negative and Gram positive bacteria. CIPTIN eradicates the biofilm of P. aeruginosa and S. aureus more efficiently than HCIP·HCl and HCIP. The in vitro toxicity and genotoxicity of CIPTIN were tested against human skin keratinocyte cells (HaCaT) (IC50 = 2.33 μM). CIPTIN exhibits 2 to 9-fold lower MIC values than its IC50 against HaCaT, while its genotoxic effect determined by micronucleus assay is equivalent to the corresponding ones of HCIP·HCl or HCIP.

A new two-electron photosensitizer, H 2 BBQ 2+ [ZnCl 4 ] 2- /[(ZnCl) 2 (μ-BBH)] (BBQ stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-quinone and BBH stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-hydroquinone), has been synthesized and the oxidation state of the ligand was determined by X-ray crystallography and NMR spectroscopy. Under light illumination the H 2 BBQ 2+ [ZnCl 4 ] 2- + ZnCl 2 is reduced quantitatively to [(ZnCl) 2 (μ-BBH)] (pH ∼ 5) oxidizing H 2 O to H 2 O 2 as is evident by trap experiments. Electrochemistry gave a reversible two-electron ligand-centered redox wave for [(ZnCl) 2 (μ-BBH)]. UV-Vis, luminescence and EPR spectroscopies reveal the slow formation of a stable quinone diradical, intermediate of the reaction. DFT calculations are in agreement with the proposed mechanism. Based on this property an aqueous {[(ZnCl) 2 (μ-BBH)]||H 2 O 2 } solar rechargeable galvanic cell has been constructed.

The initial use of ligands 2'-hydroxyacetophenone (HL 1 ), 2-hydroxybenzophenone (HL 2 ) and 2,2'-dihydroxybenzophenone (H 2 L 3 ) in iron(iii) chemistry is described. The syntheses and crystal structures are reported for five iron(iii) clusters: [Fe 10 O 4 (OMe) 14 (L 1 ) 6 (MeOH) 2 ](NO 3 ) 2 ·3MeOH (1·3MeOH), [Fe 12 O 4 (OH)(OMe) 17 (L 1 ) 8 ](ClO 4 ) 2 ·2H 2 O (2·2H 2 O), [Fe 10 O 4 (OMe) 14 Cl 4 (L 2 ) 4 (MeOH) 2 ] (3), [Fe 10 O 4 (OMe) 14 (L 2 ) 6 (py) 2 ](ClO 4 ) 2 ·MeOH (4·MeOH), where py = pyridine, and [Fe 6 O 2 (OEt) 6 (O 2 CMe) 2 (L 3 ) 2 (HL 3 ) 2 ] (5). The molecular structures of the decanuclear clusters 1, 3 and 4 are organized around a {Fe 10 (μ 4 -O) 4 (μ 3 -OMe) 2 (μ-OMe) 12 } 8+ core consisting of ten {Fe 3 O 4 } face-sharing defective cubane units. The core of 2 consists of a {Fe 12 (μ 4 -O) 4 (μ 3 -OMe) 4 (μ-OH)(μ-OMe) 13 } 10+ unit composed of twelve {Fe 3 O 4 } face-sharing defective cubanes. The ligands (L 1 ) - and (L 2 ) - in 1-4 adopt the O,O'-bidentate chelating coordination mode and their roles are to terminate the further aggregation of the Fe III /O 2- /RO - cores. Complex 5 contains the {Fe 6 (μ 4 -O) 2 (μ-OEt) 6 (μ-O carbonyl ) 2 } 4+ core, where the μ-O carbonyl atoms are the bridging carbonyl oxygens of the two η 1 :η 2 :η 1 :μ (L 3 ) 2- ligands; the (HL 3 ) - groups behave as O phenolate , O carbonyl -bidentate chelating ligands with the neutral hydroxyl group being unbound to the Fe III atoms. The core is composed of four {Fe 3 O 4 } face-sharing defective cubanes. The Fe III atoms in 1-5 are all six-coordinate with distorted octahedral geometries. The IR spectra of the complexes are discussed in terms of the known coordination modes of the ligands and the ionic character of nitrates and perchlorates. Variable-temperature magnetic susceptibility and variable-field magnetization measurements establish that 2, 3 and 5 have S = 3, 0 and 5 ground states, respectively. The susceptibility data for 5 were fitted using a 3-J model indicating the simultaneous presence of both antiferromagnetic and ferromagnetic Fe III Fe III exchange interactions. Known magnetostructural correlations in oxido-bridged iron(iii) systems have been applied to rationalise the magnetic behaviour of the three clusters. The results of the present study demonstrate the utility of HL 1 , HL 2 and H 2 L 3 in the stabilisation of robust iron(iii)/oxido/alkoxido clusters.

Platinum(ii) complexes of the formula PtLCl 2 [L = 2-(2'-pyridyl)quinoxaline, (pqx) (1), 2,(2'-pyridyl)benzo[g]quinoxaline, (pbqx) (3) and 2,(2'-pyridyl)quinoline, (pqn) (5)] were synthesized and characterized by spectroscopic and X-ray diffraction methods. Also, monodentate coordination of the ligands pqx and pbqx formed the complexes trans-Pt(DMSO)pqxCl 2 (2) and trans-Pt(DMSO)pbqxCl 2 (4) as it is indicated from X-ray crystal structure and NMR studies. The reaction of the complexes (1), (3) and (5) with DMSO-d 6 revealed a ligand-release solvolysis, which was studied by means of NMR techniques. Correlation between the crystal structures of (1), (3), and (5) and the kinetic or thermodynamic parameters of the solvolysis reactions showed that the tendency of the ligands pqx, pbqx, and pqn to return to the anti-configuration in addition to their ability to form non-classical H-bonds are crucial factors for the ligand-release solvolysis. Instantaneous DMSO-d 6 solvolysis for the complexes (1) and (3) and slow kinetics solvolysis for (5) (k = 10 -4 ± 6.4 × 10 -6 s -1 ) reflect their structural differences in ligand planarity. Based on NMR techniques a two-step mechanism of the chelate ring opening was suggested with equilibrium constants of the overall reaction at 298 K, K eq = 4.1 ± 0.2 × 10 -4 M -1 (1) and K eq = 1.7 ± 0.2 × 10 -4 M -1 (2).

The reactions of various copper(ii) sources with 2-acetylpyridine, (py)(me)CO, and 2-benzoylpyridine, (py)(ph)CO, under strongly basic conditions have been studied and novel ligand transformations have been discovered. Reaction of Cu(ClO4)2·6H2O and (py)(me)CO in the presence of NBu4(n)OMe (1 : 1 : 1) in CHCl3 gave a mixture of [Cu2Cl2(HLA)2](ClO4)2 (1) and [Cu2Cl2(LB)2(ClO4)2] (2), where HLA is 3-hydroxy-1,3-di(pyridin-2-yl)-butane-1-one and LB is the zwitterionic-type ligand 3-hydroxy-1-methyl-3-(pyridin-2-yl)-3H-indolizin-4-ium. The ligand HLA is formed through an aldol reaction-type mechanism, while the formation of LB takes place via an intramolecular nucleophilic attack of the remote 2-pyridyl nitrogen atom on the positive carbonyl carbon of HLA, after the transformation of the latter through deprotonation and dehydration. The Cu(II) ions in 1 are bridged by two 2.1111 HLA ligands resulting in a long Cu(II)Cu(II) distance (5.338 Å); the metal ions in 2 are triply bridged by the alkoxide oxygen atoms of the two 2.21 LB ligands and one 2.1100 perchlorato group. The absence of α-hydrogens in (py)(ph)CO leads the reactivity of this ligand in the presence of Cu(II) to different pathways. The Cu(ClO4)2·6H2O/(py)(ph)CO/NBu4(n)OMe reaction mixture in MeOH/H2O (25 : 1 v/v) gave the dinuclear cationic complex [Cu2{(py)(ph)CO}2(LC)2](ClO4)2 (3), where LC(-) is the anion of (methoxy)(phenyl)(pyridin-2-yl)methanol formed in situ via the nucleophilic addition of MeO(-) to the carbonyl carbon of (py)(ph)CO upon Cu(II) coordination. The Cu(II) ions in the cation are doubly bridged by the deprotonated oxygen atoms of the two LC(-) ligands. Replacement of Cu(ClO4)2·6H2O with Cu(NO3)2·3H2O and NBu4(n)OMe with NMe4OH and the decrease of the H2O concentration in the above reaction system yielded the tetranuclear coordination cluster [Cu4(OMe)2(NO3)4{(py)(ph)CO}2(LC)2] (4). The Cu(II) centres in this complex define a parallelogram. Two parallel sides of the parallelogram are each supported by deprotonated oxygen atoms belonging to a 2.21 LC(-) ligand and a 2.2 MeO(-) group. The metal ions that define each of the other two sides are singly bridged by an oxygen atom of a 2.210 nitrato group. No bridging exists between the Cu(II) ions that define the two diagonals of the parallelogram. Replacement of MeOH with EtOH in the reaction system that gave 4 resulted in the dinuclear complex [Cu2(NO3)2(LD)2)(EtOH)] (5), LD(-) being the anion of (ethoxy)(phenyl)(pyridin-2-yl)methanol. The Cu(II) ions are doubly bridged by the alkoxide oxygen atoms of the two 2.21 LD(-) ligands. The 1 : 1 : 1 Cu(NO3)2·3H2O/(py)(ph)CO/NMe4OH reaction system in CH3NO2 gave the dinuclear complex [Cu2(NO3)2(LE)2] (6), where LE(-) is the anion of 2-nitro-1-phenyl-1-(pyridin-2-yl)ethanol. The OH(-) ion abstracts one of the methyl hydrogens of CH3NO2, and once the carbanion (-):CH2NO2 is formed it attacks the positive (δ+) carbonyl carbon of (py)(ph)CO; as the carbanion forms the new C-C bond, the π electrons of the carbonyl group of the original ligand are transferred completely to oxygen forming the alkoxide-type ligand LE(-). The Cu(II) ions are doubly bridged by the alkoxide oxygen atoms of the two 2.21 LE(-) ligands. Simplified mechanistic views of the Cu(II)-assisted formation of the transformed ligands are proposed. Dc magnetic susceptibility studies in the 2-300 K range for the representative complexes 3-6 reveal the presence of very strong antiferromagnetic Cu(II)Cu(II) exchange interactions in the dinuclear complexes 3, 5, and 6 and within the dimeric {Cu2(OMe)(NO3){(py)(ph)CO}(LC)}(+) subunits of 4. The strong antiferromagnetic coupling is discussed in terms of the large Cu-O-Cu angles (101.0-102.9°) in the dinuclear, planar {Cu2O2} units/subunits of 3-6.

Five novel pentanuclear Fe(3+) clusters with the aliphatic amino-alcohol ligands 3-amino-1-propanol (Hap) and 2-(hydroxymethyl)piperidine (Hhmpip) [Fe(5)(μ(3)-Ο)(2)(L)(4)(O(2)CR)(7)] [L = ap(-), R = Ph (1); L = ap(-), R = C(CH(3))(3) (2); L = hmpip(-), R = Ph (3); L = hmpip(-), R = C(CH(3))(3) (4)] and [Fe(5)(μ(4)-Ο)(μ(3)-Ο)(O(2)CC(CH(3))(3))(8)(ap)(2)Cl(HO(2)CC(CH(3))(3))] (5) are reported. Compounds 1-4 were prepared from reactions of preformed trinuclear Fe(3+) clusters with the ligands in a molar ratio 1 : 5 in MeCN (1, 3, 4) or DMF (2), whereas compound 5 was prepared from the reaction of FeCl(3) with Hap in the presence of HO(2)CC(CH(3))(3) in a molar ratio 1 : 3 : 2 in MeCN. To the best of our knowledge, 1-5 are the first examples of Fe(3+) complexes with the ligands Hap and Hhmpip. The structures of 1-4 are composed of a quasi-planar [Fe(5)(μ(3)-O)(2)](11+) core which consists of two vertex-sharing [Fe(3)(μ(3)-O)](7+) triangles. The structure of 5 is based on the [Fe(5)(μ(4)-O)(μ(3)-O)](11+) core, in which the five Fe(3+) ions adopt a monocapped trigonal pyramidal topology. Variable-temperature magnetic susceptibility measurements on powdered microcrystalline samples of 1 and 5 revealed the existence of antiferromagnetic interactions which led to an S = 5/2 ground state. Mössbauer spectroscopy studies on powdered microcrystalline samples of 1 and 5 confirmed that all iron ions of both complexes are in the Fe(3+) (S = 5/2) state. The variation of the ligand environment in the various iron sites was reflected in their different quadruple splitting parameters. At T < 50 K the Mössbauer spectra indicated the onset of spin relaxation effects in the time scale of the technique (10(-7)-10(-8) s).

Two new Mn(15) clusters consisting of a supertetrahedron which is incorporated in a loop are reported. The reactions of [Mn(O(2)CEt)(2)]·2H(2)O with the diols 1,3-propanediol (H(2)pd) or 2-methyl-1,3-propanediol (H(2)mpd) in the presence of KX (X = CN(-), Cl(-), Br(-), NO(3)(-), ClO(4)(-), OCN(-), SCN(-)) afforded compounds [Mn(15)K(mu(4)-O)(4)(O(2)CEt)(11)(pd)(12)(py)(2)] (1) and [Mn(15)K(mu(4)-O)(4)(O(2)CEt)(11)(mpd)(12)(py)(2)] (2). The structural core of 1 and 2 consists of a Mn(11) loop and a Mn(9)K supertetrahedron sharing a Mn(5) triangle. To the best of our knowledge, the structural motif of a supertetrahedron incorporated in a loop appears for the first time in metal cluster chemistry. Variable-temperature, solid-state direct current (dc) magnetic susceptibility studies in the 300-5 K range showed that the chi(M)T value increases with decreasing T suggesting the existence of predominant ferromagnetic exchange interactions and a relatively large ground state spin. This was confirmed by field-variable temperature magnetization measurements which were fitted using a matrix diagonalization method to give S approximately 23/2, g = 1.92(1) and D = -0.071(2) cm(-1). In addition, compound 1 displays frequency-dependent alternating current (ac) signals suggesting single-molecule magnetism (SMM) behaviour. This was proven by magnetization vs. dc field sweeps on single-crystals of 1·0.7py·1.3MeCN, which displayed sweep rate- and temperature-dependent hysteresis loops.

The reaction of Cu2+ acetate monohydrate with 2-[N,N'-bis(carboxymethyl)aminomethyl]-4-carboxyphenol (H4cacp), 2-[N,N-bis(carboxymethyl)aminomethyl]hydroquinone (H4cah) and the dinucleating 2,5-bis[N,N-bis(carboxymethyl)aminomethyl]hydroquinone (H6bicah) in water results in the formation of several Cu2+ species, which are in dynamic equilibrium in aqueous solution and their stability is pH dependent. A systematic crystallographic study of these species was pursued, resulting in the characterization of most of the species. Additional techniques were employed to characterize the molecules in the solid state (infrared spectroscopy) and in solution (UV-vis spectroscopy and electrochemistry). These measurements show that the Cu2+ ions are ligated mainly to the iminodiacetate at pH < 6, exhibiting only weak interactions with the phenol oxygen. At pH > 6, the phenol oxygen was deprotonated and dinuclear-bridged species, from the phenolate oxygen complexes exhibiting a Cu2+ 2O2 core, were isolated. The coordination environment around the copper ions varies between trigonal bipyramidal, tetragonal pyramidal and distorted octahedral geometries. The two unpaired electrons of the Cu2+ ions are found to be antiferromagnetically coupled. A survey of the magnetic and structural properties of the dinuclear phenoxide bridged Cu2+ complexes shows that the strength of the antiferromagnetic coupling is linearly dependent on the Cu-Ophenolate bond lengths, at bond distances below 1.98 angstroms. The effect of the Cu-O-Cu angles on the magnetic properties of the complexes is also discussed.

The combination of diol-type ligands with paramagnetic transition metal ions has led to the isolation of a host of new homometallic and heterometallic clusters, high-spin molecules and single molecule magnets ranging in nuclearity from two to forty four and with spin ground states as large as S = 61/2. The ligands, whose cluster coordination chemistry is discussed in this article, are 1,3-propanediol and its derivatives, diethanolamine and its derivatives, pyridine-2,6-dimethanol and the gem-diol form of di-2-pyridyl ketone. The structural diversity of the complexes stems from the ability of the ligands to adopt a variety of bridging coordination modes depending on the positions of the two hydroxyl groups in the molecule, the presence/absence of extra donor groups and on the reaction conditions. Examples of 'true' reactivity chemistry involving clusters of diol-type ligands are also given. The activation of pyridine-2,6-dimethanol and di-2-pyridyl ketone by 3d-metal centres towards further reactions seems to be an emergent area of synthetic chemistry.