A series of M(II)Cu(II)3 stars (M = Mn, Ni, Cu, Zn) exhibiting unusual magnetic properties.

The work in this report describes the syntheses, electrospray ionization mass spectromtery, structures, and experimental and density functional theoretical (DFT) magnetic properties of four tetrametallic stars of composition [M(II)(Cu(II)L)3](ClO4)2 (1, M = Mn; 2, M = Ni; 3, M = Cu; 4, M = Zn) derived from a single-compartment Schiff base ligand, N,N'-bis(salicylidene)-1,4-butanediamine (H2L), which is the [2 + 1] condensation product of salicylaldehyde and 1,4-diaminobutane. The central metal ion (Mn(II), Ni(II), Cu(II), or Zn(II)) is linked with two µ2-phenoxo bridges of each of the three [Cu(II)L] moieties, and thus the central metal ion is encapsulated in between three [Cu(II)L] units. The title compounds are rare or sole examples of stars having these metal-ion combinations. In the cases of 1, 3, and 4, the four metal ions form a centered isosceles triangle, while the four metal ions in 2 form a centered equilateral triangle. Both the variable-temperature magnetic susceptibility and variable-field magnetization (at 2-10 K) of 1-3 have been measured and simulated contemporaneously. While the Mn(II)Cu(II)3 compound 1 exhibits ferromagnetic interaction with J = 1.02 cm(-1), the Ni(II)Cu(II)3 compound 2 and Cu(II)Cu(II)3 compound 3 exhibit antiferromagnetic interaction with J = -3.53 and -35.5 cm(-1), respectively. Variable-temperature magnetic susceptibility data of the Zn(II)Cu(II)3 compound 4 indicate very weak antiferromagnetic interaction of -1.4 cm(-1), as expected. On the basis of known correlations, the magnetic properties of 1-3 are unusual; it seems that ferromagnetic interaction in 1 and weak/moderate antiferromagnetic interaction in 2 and 3 are possibly related to the distorted coordination environment of the peripheral copper(II) centers (intermediate between square-planar and tetrahedral). DFT calculations have been done to elucidate the magnetic properties. The DFT-computed J values are quantitatively (for 1) or qualitatively (for 2 and 3) matched well with the experimental values. Spin densities and magnetic orbitals (natural bond orbitals) correspond well with the trend of observed/computed magnetic exchange interactions.

A very rare fluorescent chemosensor of zinc(II) exhibiting AIEE, ESIPT and TICT: Spectroscopic, crystallographic and theoretical exploration.

The basic systems in this study are HL (1; 1:2 condensation product of 2,6-diformyl-4-ethylphenol and o-anisidine) and its ZnII and CdII complexes of composition [ZnII(LH)Cl2]·CH3OH (2) and [CdII(LH)Cl2] (3), all of which are synthesized and characterized by CHN elemental analyses, single crystal X-ray crystallography, powder X-ray diffraction (PXRD) and fourier transform infrared (FT-IR) spectrum. It has been established from the following experimental and theoretical studies that 1 is a fluorescent turn on sensor of ZnII ion and it exhibits all of excited state intramolecular proton transfer (ESIPT), photoinduced electron transfer (PET), twisted intramolecular charge transfer (TICT) and aggregation induced enhanced emission (AIEE): (i) Detailed absorption and emission (steady state / time resolved) studies in various single solvents, in solvent mixtures, with pH variation, with various single metal ions, with mixtures of metal ions, on varying temperature and on varying viscosity; (ii) dynamic light scattering (DLS) and scanning electron microscopy (SEM) in solvent mixtures; (iii) density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations in ground and excites states of 1-3. It is shown that 1 can be efficaciously applied in inkless writing with the "write - erase - write" facility. The mechanisms/reasons of the observed properties have been addressed. The difference in fluorescence of ZnII and CdII complexes, unusual case of crystal structures of probe and complexes with ZnII and CdII, unusual features in the structures of 2 and 3 as well as a structure-property correlation have been discussed.

Structures, magnetochemistry, spectroscopy, theoretical study, and catechol oxidase activity of dinuclear and dimer-of-dinuclear mixed-valence Mn(III)Mn(II) complexes derived from a macrocyclic ligand.

The work in this paper presents syntheses, characterization, magnetic properties (experimental and density functional theoretical), catecholase activity, and electrospray ionization mass spectroscopic (ESI-MS positive) studies of two mixed-valence dinuclear Mn(III)Mn(II) complexes, [Mn(III)Mn(II)L(µ-O2CMe)(H2O)2](ClO4)2·H2O·MeCN (1) and [Mn(III)Mn(II)L(µ-O2CPh)(MeOH)(ClO4)](ClO4) (2), and a Mn(III)Mn(II)Mn(II)Mn(III) complex, [{Mn(III)Mn(II)L(µ-O2CEt)(EtOH)}2(µ-O2CEt)](ClO4)3 (3), derived from the Robson-type macrocycle H2L, which is the [2 + 2] condensation product of 2,6-diformyl-4-methylphenol and 2,2-dimethyl-1,3-diaminopropane. In 1 and 2 and in two Mn(III)Mn(II) units in 3, the two metal centers are bridged by a bis(µ-phenoxo)-µ-carboxylate moiety. The two Mn(II) centers of the two Mn(III)Mn(II) units in 3 are bridged by a propionate moiety, and therefore this compound is a dimer of two dinuclear units. The coordination geometry of the Mn(III) and Mn(II) centers are Jahn-Teller distorted octahedral and distorted trigonal prism, respectively. Magnetic studies reveal weak ferro- or antiferromagnetic interactions between the Mn(III) and Mn(II) centers in 1 (J = +0.08 cm(-1)), 2 (J = -0.095 cm(-1)), and 3 (J1 = +0.015 cm(-1)). A weak antiferromagnetic interaction (J2 = -0.20 cm(-1)) also exists between the Mn(II) centers in 3. DFT methods properly reproduce the nature of the exchange interactions present in such systems. A magneto-structural correlation based on Mn-O bridging distances has been proposed to explain the different sign of the exchange coupling constants. Utilizing 3,5-di-tert-butyl catechol (3,5-DTBCH2) as the substrate, catecholase activity of all the three complexes has been checked in MeCN and MeOH, revealing that all three are active catalysts with Kcat values lying in the range 7.5-64.7 h(-1). Electrospray ionization mass (ESI-MS positive) spectra of the complexes 1-3 have been recorded in MeCN solutions, and the positive ions have been well characterized. ESI-MS positive spectrum of complex 1 in presence of 3,5-DTBCH2 has also been recorded, and a positive ion, [Mn(III)Mn(II)L(µ-3,5-DTBC(2-))](+), having most probably a bridging catecholate moiety has been identified.

Syntheses, structures, magnetic properties, and density functional theory magneto-structural correlations of bis(µ-phenoxo) and bis(µ-phenoxo)-µ-acetate/bis(µ-phenoxo)-bis(µ-acetate) dinuclear Fe(III)Ni(II) compounds.

The bis(µ-phenoxo) Fe(III)Ni(II) compound [Fe(III)(N3)2LNi(II)(H2O)(CH3CN)](ClO4) (1) and the bis(µ-phenoxo)-µ-acetate/bis(µ-phenoxo)-bis(µ-acetate) Fe(III)Ni(II) compound {[Fe(III)(OAc)LNi(II)(H2O)(µ-OAc)](0.6)·[Fe(III)LNi(II)(µ-OAc)2](0.4)}(ClO4)·1.1H2O (2) have been synthesized from the Robson type tetraiminodiphenol macrocyclic ligand H2L, which is the [2 + 2] condensation product of 4-methyl-2,6-diformylphenol and 2,2'-dimethyl-1,3-diaminopropane. Single-crystal X-ray structures of both compounds have been determined. The cationic part of the dinuclear compound 2 is a cocrystal of the two species [Fe(III)(OAc)LNi(II)(H2O)(µ-OAc)](+) (2A) and [Fe(III)LNi(II)(µ-OAc)2](+) (2B) with weights of 60% of the former and 40% of the latter. While 2A is a triply bridged bis(µ-phenoxo)-µ-acetate system, 2B is a quadruply bridged bis(µ-phenoxo)-bis(µ-acetate) system. Variable-temperature (2-300 K) magnetic studies reveal antiferromagnetic interaction in 1 and ferromagnetic interaction in 2 with J values of -3.14 and 7.36 cm(-1), respectively (H = -2JS1·S2). Broken-symmetry density functional calculations of exchange interaction have been performed on complexes 1 and 2 and also on previously published related compounds, providing good numerical estimates of J values in comparison to experiments. The electronic origin of the difference in magnetic behavior of 1 and 2 has been well understood from MO analyses and computed overlap integrals of BS empty orbitals. The role of acetate and thus its complementarity/countercomplementarity effect on the magnetic properties of diphenoxo-bridged Fe(III)Ni(II) compounds have been determined on computing J values of model compounds by replacing bridging acetate and nonbridging acetate ligand(s) by water ligands in the model compounds derived from 2A,B. The DFT calculations have also been extended to develop several magneto-structural correlations in these types of complexes, and the correlations focus on the role of Fe-O-Ni bridge angle, average Fe/Ni-O bridge distance, Fe-O-Ni-O dihedral angle, and out-of-plane shift of the phenoxo group.

Syntheses, structures, and steady state and time resolved photophysical properties of a tetraiminodiphenol macrocyclic ligand and its dinuclear zinc(II)/cadmium(II) complexes with coordinating and noncoordinating anions.

The work in the present investigation reports the syntheses, structures, steady state, and time-resolved photophysical properties of a tetraiminodiphenol macrocyclic ligand H(2)L and its eight dinuclear zinc(II) complexes and one cadmium(II) complex having composition [Zn(2)L(H(2)O)(2)](ClO(4))(2)·2CH(3)CN (1), [Zn(2)L(H(2)O)(2)](ClO(4))(2)·2dmf (2), [Zn(2)L(H(2)O)(2)](NO(3))(2)·2dmf (3), [Zn(2)LCl(2)] (4), [Zn(2)L(N(3))(2)] (5), [Zn(2)L(NCS)(2)] (6), [Zn(2)L(NCO)(2)] (7), [Zn(2)L(NCSe)(2)](2)·dmf (8), and [Cd(2)L(OAc)(2)] (9) with various coordinating and noncoordinating anions. The structures of all the complexes 1-9 have been determined by single-crystal X-ray diffraction. The noncovalent interactions in the complexes result in the generation of the following topologies: two-dimensional network in 1, 2, 4, 6, 7, 8, and 9; three-dimensional network in 5. Spectrophotometric and spectrofluorometric titrations of the diprotonated salt [H(4)L](ClO(4))(2) with triethylamine as well as with zinc(II) acetate and cadmium(II) acetate have been carried out, revealing fluorescence enhancement of the macrocyclic system by the base and the metal ions. Steady state fluorescence properties of [H(4)L](ClO(4))(2) and 1-9 have been studied and their quantum yields have been determined. Time resolved fluorescence behavior of [H(4)L](ClO(4))(2) and the dizinc(II) and dicadmium(II) complexes 1-9 have also been studied, and their lifetimes and radiative and nonradiative rate constants have been determined. The induced fluorescence enhancement of the macrocycle by zinc(II) and cadmium(II) is in line with the greater rate of increase of the radiative rate constants in comparison to the smaller rate of increase of nonradiative rate constants for the metal complexes. The fluorescence decay profiles of all the systems, being investigated here, that is, [H(4)L](ClO(4))(2) and 1-9, follow triexponential patterns, revealing that at least three conformers/components are responsible to exhibit the fluorescence decay behavior. The systems and studies in this report have been compared with those in the reports of the previously published similar systems, revealing some interesting aspects.

A metal complex based fluorescent chemodosimeter for selective detection of 2,4-dinitrophenol and picric acid in aqueous media.

This work describes the syntheses, characterization, crystal structures, absorption and emission spectra and DFT calculations of three dizinc(II) compounds of the composition [ZnII2L(µ1,1-N3)(N3)2] (1) [Zn2L'(2,4-dinitrophenolate)2] (2) and [Zn2L'(picrate)2] (3), respectively, (where HL is the 1 : 2 condensation product of 4-ethyl-2,6-diformylphenol and N-methylethylenediamine and H2L' (a diamino-diimino-diphenol system) is a new type of macrocyclic ligand). Compound 1 is water soluble and its aqueous solution exhibits intense fluorescence properties. 2,4-Dinitrophenol (DNP) and picric acid (PA) selectively quench the fluorescence intensity of 1 to a significant extent, revealing that 1 is a fluorescence sensor of DNP and PA. Compounds 2 and 3 were prepared by mixing 1 with DNP and PA. As a huge change in the system (acyclic to macrocyclic) occurs while exhibiting sensing behaviour, it is evident that 1 senses DNP and PA through a chemodosimetric approach in aqueous media. For sensing nitroaromatic compounds, compound 1 acts as (i) a rare chemodosimeter, (ii) a rare metal containing chemodosimeter and (iii) a rare fluorescent chemosensor in aqueous media. Based on the ESI-MS and single crystal X-ray structures, it has been possible to establish a mechanism for the conversion of the acyclic system in 1 to a new type of macrocyclic system in 2 and 3. It has been established from DFT calculations that ground state complexation via charge transfer and IFE can be considered as the major reason for the DNP/PA stimulated strong fluorescence quenching.

Experimental and theoretical investigations on three DyIII4 single molecule magnets: structural and magneto-structural correlations.

The work in this report describes the syntheses, crystal structures, dc/ac magnetic behaviour, and theoretical calculations (both ab initio CASSCF and DFT) of three defect dicubane/planar butterfly type tetradysprosium(III) compounds of compositions [DyIII4L4(µ3-OH)2(carboxylate)2(dmf)2] (carboxylate = formate (1), acetate (2), propionate (3)), where H2L = 2-(2-hydroxy-3-ethoxybenzylideneamino)phenol. In the butterfly type structures, two DyIII centres (Dyb) occupy the body positions while two other (Dyw) units occupy the wing positions. SHAPE analyses reveal that the coordination geometries of the Dyb and Dyw centres, both octacoordinated, are triangular dodecahedron (TDD) and square antiprism (SAPR), respectively. Variable-temperature magnetic susceptibility measurements give an indication of weak antiferromagnetic interactions and variable-field magnetization measurements reveal strong anisotropy in all the three compounds. The variable-temperature/frequency in-phase/out-of-phase AC susceptibility data reveal that all these three compounds are SMMs with two relaxation channels under zero dc field; slow relaxation (SR) and fast relaxation (FR) processes could be assigned to the SAPR (Dyw) and TDD (Dyb) metal centres, respectively. The simulated Ueff and τ0 values are: 49.0 cm-1 and 1.76 × 10-7 s for 1, 30.3 cm-1 and 1.51 × 10-8 s for 2 and 23.4 cm-1 and 9.64 × 10-7 s for 3. Furthermore, ab initio CASSCF/RASSI-SO/SINGLE_ANISO calculations reveal that the ground state of DyIII centres are axial in nature with a dominating contribution from mJ = |±15/2>. The magnetization relaxation occurs via the first excited KD resulting in the large computed blocking barrier of Dyw (SAPR) centres compared to that of the Dyb (TDD) centres which corroborates the experimental measurements. The exchange parameters obtained from DFT calculations are generally in line with those obtained from the fitting of χMT vs. T in POLY_ANISO calculations. Interesting structural and magneto-structural correlations have been found, which are the major outcomes of this investigation.

Syntheses, structures, and magnetic properties of three one-dimensional end-to-end azide/cyanate-bridged copper(II) compounds exhibiting ferromagnetic interaction: new type of solid state isomerism.

The work in this paper presents the syntheses, structures, and magnetic properties of three end-to-end (EE) azide/cyanate-bridged copper(II) compounds [Cu(II)L(1)(µ(1,3)-NCO)](n)·2nH(2)O (1), [Cu(II)L(1)(µ(1,3)-N(3))](n)·2nH(2)O (2), and [Cu(II)L(2)(µ(1,3)-N(3))](n) (3), where the ligands used to achieve these species, HL(1) and HL(2), are the tridentate Schiff base ligands obtained from [1 + 1] condensations of salicylaldehyde with 4-(2-aminoethyl)-morpholine and 3-methoxy salicylaldehyde with 1-(2-aminoethyl)-piperidine, respectively. Compounds 1 and 2 crystallize in the monoclinic P2(1)/c space group, while compound 3 crystallizes in the orthorhombic Pbca space group. The metal center in 1-3 is in all cases pentacoordinated. Three coordination positions of the metal center in 1, 2, or 3 are satisfied by the phenoxo oxygen atom, imine nitrogen atom, and morpholine (for 1 and 2) or piperidine (for 3) nitrogen atom of one deprotonated ligand, [L(1)](-) or [L(2)](-). The remaining two coordination positions are satisfied by two nitrogen atoms of two end-to-end bridging azide ligands for 2 and 3 and one nitrogen atom and one oxygen atom of two end-to-end bridging cyanate ligands for 1. The coordination geometry of the metal ion is distorted square pyramidal in which one EE azide/cyanate occupies the apical position. Variable-temperature (2-300 K) magnetic susceptibilities of 1-3 have been measured under magnetic fields of 0.05 (from 2 to 30 K) and 1.0 T (from 30 to 300 K). The simulation reveals a ferromagnetic interaction in all three compounds with J values of +0.19 ± 0.01, +0.79 ± 0.01, and +1.25 ± 0.007 cm(-1) for 1, 2, and 3, respectively. Compound 1 is the sole example of a ferromagnetically coupled EE cyanate-bridged 1-D copper(II) system. In addition, a rare example of supramolecular isomerism and a nice example of magnetic isomerism have been observed and most interestingly a new type of solid state isomerism has emerged as a result of the comparison of the structure and magnetic properties of 2 with a previously published compound (2A) having the same composition and even the same crystal system and space group (New J. Chem.2001, 25, 1203-1207).

Heterobridged dinuclear, tetranuclear, dinuclear-based 1-d, and heptanuclear-based 1-D complexes of copper(II) derived from a dinucleating ligand: syntheses, structures, magnetochemistry, spectroscopy, and catecholase activity.

The work in this paper presents syntheses, characterization, crystal structures, variable-temperature/field magnetic properties, catecholase activity, and electrospray ionization mass spectroscopic (ESI-MS positive) study of five copper(II) complexes of composition [Cu(II)(2)L(µ(1,1)-NO(3))(H(2)O)(NO(3))](NO(3)) (1), [{Cu(II)(2)L(µ-OH)(H(2)O)}(µ-ClO(4))](n)(ClO(4))(n) (2), [{Cu(II)(2)L(NCS)(2)}(µ(1,3)-NCS)](n) (3), [{Cu(II)(2)L(µ(1,1)-N(3))(ClO(4))}(2)(µ(1,3)-N(3))(2)] (4), and [{Cu(II)(2)L(µ-OH)}{Cu(II)(2)L(µ(1,1)-N(3))}{Cu(II)(µ(1,1)-N(3))(4)(dmf)}{Cu(II)(2)(µ(1,1)-N(3))(2)(N(3))(4)}](n)·ndmf (5), derived from a new compartmental ligand 2,6-bis[N-(2-pyridylethyl)formidoyl]-4-ethylphenol, which is the 1:2 condensation product of 4-ethyl-2,6-diformylphenol and 2-(2-aminoethyl)pyridine. The title compounds are either of the following nuclearities/topologies: dinuclear (1), dinuclear-based one-dimensional (2 and 3), tetranuclear (4), and heptanuclear-based one-dimensional (5). The bridging moieties in 1-5 are as follows: µ-phenoxo-µ(1,1)-nitrate (1), µ-phenoxo-µ-hydroxo and µ-perchlorate (2), µ-phenoxo and µ(1,3)-thiocyanate (3), µ-phenoxo-µ(1,1)-azide and µ(1,3)-azide (4), µ-phenoxo-µ-hydroxo, µ-phenoxo-µ(1,1)-azide, and µ(1,1)-azide (5). All the five compounds exhibit overall antiferromagnetic interaction. The J values in 1-4 have been determined (-135 cm(-1) for 1, -298 cm(-1) for 2, -105 cm(-1) for 3, -119.5 cm(-1) for 4). The pairwise interactions in 5 have been evaluated qualitatively to result in S(T) = 3/2 spin ground state, which has been verified by magnetization experiment. Utilizing 3,5-di-tert-butyl catechol (3,5-DTBCH(2)) as the substrate, catecholase activity of all the five complexes have been checked. While 1 and 3 are inactive, complexes 2, 4, and 5 show catecholase activity with turn over numbers 39 h(-1) (for 2), 40 h(-1) (for 4), and 48 h(-1) (for 5) in dmf and 167 h(-1) (for 2) and 215 h(-1) (for 4) in acetonitrile. Conductance of the dmf solution of the complexes has been measured, revealing that bridging moieties and nuclearity have been almost retained in solution. Electrospray ionization mass (ESI-MS positive) spectra of complexes 1, 2, and 4 have been recorded in acetonitrile solutions and the positive ions have been well characterized. ESI-MS positive spectrum of complex 2 in presence of 3,5-DTBCH(2) have also been recorded and, interestingly, a positive ion [Cu(II)(2)L(µ-3,5-DTBC(2-))(3,5-DTBCH(-))Na(I)](+) has been identified.

Magnetic exchange interactions and magneto-structural correlations in heterobridged µ-phenoxo-µ(1,1)-azide dinickel(II) compounds: a combined experimental and theoretical exploration.

This investigation presents the syntheses, crystal structures, magnetic properties, and density functional theoretical modeling of magnetic behavior of two heterobridged µ-phenoxo-µ(1,1)-azido dinickel(II) compounds [Ni(II)(2)(L(1))(2)(µ(1,1)-N(3))(N(3))(H(2)O)]·CH(3)CH(2)OH (1) and [Ni(II)(2)(L(2))(2)(µ(1,1)-N(3))(CH(3)CN)(H(2)O)](ClO(4))·H(2)O·CH(3)CN (2), where HL(1) and HL(2) are the [1+1] condensation products of 3-methoxysalicylaldehyde and 1-(2-aminoethyl)-piperidine (for HL(1))/4-(2-aminoethyl)-morpholine (for HL(2)), along with density functional theoretical magneto-structural correlations of µ-phenoxo-µ(1,1)-azido dinickel(II) systems. Compounds 1 and 2 crystallize in orthorhombic (space group Pbca) and monoclinic (space group P2(1)/c) systems, respectively. The coordination environments of both metal centers are distorted octahedral. The variable-temperature (2-300 K) magnetic susceptibilities at 0.7 T of both compounds have been measured. The interaction between the metal centers is moderately ferromagnetic; J = 16.6 cm(-1), g = 2.2, and D = -7.3 cm(-1) for 1 and J = 16.92 cm(-1), g = 2.2, and D(Ni1) = D(Ni2) = -6.41 cm(-1) for 2. Broken symmetry density functional calculations of exchange interaction have been performed on complexes 1 and 2 and provide a good numerical estimate of J values (15.8 cm(-1) for 1 and 15.35 cm(-1) for 2) compared to experiments. The role of Ni-N bond length asymmetry on the magnetic coupling has been noted by comparing the structures and J values of complexes 1 and 2 together with previously published dimers 3 (Eur. J. Inorg. Chem. 2009, 4982), 4 (Inorg. Chem. 2004, 43, 2427), and 5 (Dalton Trans. 2008, 6539). Our extensive DFT calculations reveal an important clue to the mechanism of coupling where the orientation of the magnetic orbitals seems to differ with asymmetry in the Ni-N bond lengths. This difference in orientation leads to a large change in the overlap integral between the magnetic orbitals and thus the magnetic coupling. DFT calculations have also been extended to develop several magneto-structural correlations in this type of complexes and the correlation aim to focus on the asymmetry of the Ni-N bond lengths reveal that the asymmetry plays a proactive role in governing the magnitude of the coupling. From a completely symmetric Ni-N bond length, two behaviors have been noted: with a decrease in bond length there is an increase in the ferromagnetic coupling, while an increase in the bond lengths leads to a decrease in ferromagnetic interaction. The later correlation is supported by experiments. The magnetic properties of 1, 2, and three previously reported related compounds have been discussed in light of the structural parameters and also in light of the theoretical correlations determined here.

Slow magnetic relaxation and electron delocalization in an S = 9/2 iron(II∕III) complex with two crystallographically inequivalent iron sites.

The magnetic, electronic, and Mössbauer spectral properties of [Fe(2)L(µ-OAc)(2)]ClO(4), 1, where L is the dianion of the tetraimino-diphenolate macrocyclic ligand, H(2)L, indicate that 1 is a class III mixed valence iron(II∕III) complex with an electron that is fully delocalized between two crystallographically inequivalent iron sites to yield a [Fe(2)](V) cationic configuration with a S(t) = 9∕2 ground state. Fits of the dc magnetic susceptibility between 2 and 300 K and of the isofield variable-temperature magnetization of 1 yield an isotropic magnetic exchange parameter, J, of -32(2) cm(-1) for an electron transfer parameter, B, of 950 cm(-1), a zero-field uniaxial D(9∕2) parameter of -0.9(1) cm(-1), and g = 1.95(5). In agreement with the presence of uniaxial magnetic anisotropy, ac susceptibility measurements reveal that 1 is a single-molecule magnet at low temperature with a single molecule magnetic effective relaxation barrier, U(eff), of 9.8 cm(-1). At 5.25 K the Mössbauer spectra of 1 exhibit two spectral components, assigned to the two crystallographically inequivalent iron sites with a static effective hyperfine field; as the temperature increases from 7 to 310 K, the spectra exhibit increasingly rapid relaxation of the hyperfine field on the iron-57 Larmor precession time of 5 × 10(-8) s. A fit of the temperature dependence of the average effective hyperfine field yields |D(9∕2)| = 0.9 cm(-1). An Arrhenius plot of the logarithm of the relaxation frequency between 5 and 85 K yields a relaxation barrier of 17 cm(-1).

Syntheses, structures, and magnetic properties of diphenoxo-bridged Cu(II)Ln(III) and Ni(II)(low-spin)Ln(III) compounds derived from a compartmental ligand (Ln = Ce-Yb).

Syntheses, characterization, and magnetic properties of a series of diphenoxo-bridged discrete dinuclear M(II)Ln(III) complexes (M = Cu or Ni, Ln = Ce-Yb) derived from the compartmental Schiff base ligand, H(2)L, obtained on condensation of 3-ethoxysalicylaldehyde with trans-1,2-diaminocyclohexane, are described. Single crystal X-ray structures of eight Cu(II)Ln(III) compounds (Ln = Ce (1), Pr (2), Nd (3), Sm (4), Tb (7), Ho (9), Er (10), and Yb (12)) and three Ni(II)Ln(III) (Ln = Ce (13), Sm (16), and Gd (18)) compounds have been determined. Considering the previously reported structure of the Cu(II)Gd(III) (6) compound (Eur. J. Inorg. Chem. 2005, 1500), a total of twelve structures are discussed/compared in this study. Four types of composition are observed in the Cu(II)Ln(III) complexes: [Cu(II)LLn(III) (NO(3))(3)(H(2)O)] (1-3: Ln = Ce-Nd), [Cu(II)LSm(III)(NO(3))(3)]·CH(3)COCH(3) (4), [Cu(II)(H(2)O)LLn(III)(NO(3))(3)] (5: Ln = Eu; 6: Ln = Gd), and [Cu(II)LLn(III)(NO(3))(3)] (4A: Ln = Sm; 7-12: Ln = Tb-Yb). On the other hand, the Ni(II)Ln(III) complexes are characterized to have two types of composition: [Ni(II)LLn(III)(H(2)O)(NO(3))(3)] (13-15: Ln = Ce-Nd) and [Ni(II)LLn(III)(NO(3))(3)]·0.5CH(3)COCH(3) (16-24: Ln = Sm-Yb). Among twelve X-ray structures, seven belong to three different isomorphous sets (Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13); Cu(II)Tb(III) (7), Cu(II)Ho(III) (9), Cu(II)Er(III) (10), and Cu(II)Yb(III) (12); Ni(II)Sm(III) (16) and Ni(II)Gd(III) (18)), whereas space group/unit cell parameters of two others (Cu(II)Sm(III) (4) and Cu(II)Gd(III) (6)) are of different types. The lanthanide(III) centers in Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13) complexes are eleven-coordinated, while the lanthanide(III) centers in other compounds are ten-coordinated. As evidenced from the dihedral angle (δ) between the CuO(phenoxo)(2) and LnO(phenoxo)(2) planes, variation in the extent of planarity of the bridging moiety in the Cu(II)Ln(III) compounds takes place; the ranges of δ values are 0.8-6.2° in the 4f(1-7) analogues and 17.6-19.1° in the 4f(8-13) analogues. The Cu(II)Gd(III) (6) compound exhibits ferromagnetic interaction (Eur. J. Inorg. Chem. 2005, 1500). The nature of the magnetic exchange interaction in the Cu(II)Ln(III) complexes has been understood by utilizing the empirical approach; the Ni(II)Ln(III) complexes have been used as references. The metal centers in the Eu(III) complex are uncorrelated, while other 4f(1-6) analogues (Ce(III), Pr(III), Nd(III), and Sm(III)) exhibit antiferromagnetic interaction. Among the higher analogues (4f(7-13)), only Yb(III) exhibits antiferromagnetic interaction, while interaction in other analogues (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), and Tm(III)) is ferromagnetic. An important aspect of the present study is the measurement of the magnetic susceptibility of the unblocked samples as well as on blocking the samples with grease to avoid powder reorientation, if any. Comparison of the two sets of data reveals significant difference in some cases.

Magneto-structural correlation studies and theoretical calculations of a unique family of single end-to-end azide-bridged Ni(II)4 cyclic clusters.

The work in this paper aims to portray a complete structural, magnetic, and theoretical description of two original end-to-end (EE) µ(1,3)-azide-bridged, cyclic tetranuclear Ni(II) clusters, [{Ni(II)(L(1))(µ(1,3)-N(3))(H(2)O)}(4)] (1) and [{Ni(II)(L(2))(µ(1,3)-N(3))(H(2)O)}(4)] (2), where the ligands used to achieve these species, HL(1) and HL(2), are the tridentate Schiff base ligands obtained from [1 + 1] condensations of salicylaldehyde with 1-(2-aminoethyl)-piperidine and 4-(2-aminoethyl)-morpholine, respectively. The title compounds, 1 and 2, crystallize in a monoclinic P2(1) space group. Overall, both species can be described in a similar way; where all Ni(II) centers within each molecule are hexacoordinated and bound to [L(1)](-) or [L(2)](-) through the phenoxo oxygen, imine nitrogen, and piperidine/morpholine nitrogen atoms of the corresponding ligand. The remaining coordination sites are satisfied by one molecule of H(2)O and two nitrogen atoms from N(3)(-) anions. The latest act as bridges between Ni(II) ions, and eventually, only four azido groups are linked to the same number of Ni(II) centers resulting in the formation of cyclic Ni(II)(4) systems. Interestingly, compounds 1 and 2 are the two sole examples of tetranuclear clusters generated exclusively by EE azide-bridging ligands to date. All the N(azide)-Ni-N(azide) moieties are almost linear in 1 and 2 indicating trans arrangement of the azido ligand. Variable-temperature (2-300 K) magnetic susceptibilities of 1 and 2 have been measured under magnetic fields of 0.04 T (from 2 to 30 K) and 0.7 T (from 30 to 300 K), and magneto-structural correlations have been performed. Despite the presence of both ferromagnetic and antiferromagnetic interactions in both compounds, significant differences have been observed in their magnetic behaviors directly related to the arrangement of the bridging azido ligands. Hence, compound 1 has an overall moderate antiferromagnetic behavior due to the presence of an exchange pathway with an unprecedented Ni-N···N-Ni torsion angle close to 0°, meanwhile complex 2 exhibits a predominant ferromagnetic behavior, with torsion angles between 50 and 90°. Density functional theory calculations have been performed to provide more insight into the magnetic nature of this new family of Ni(II)-azido complexes and also to corroborate the fitting of the data.

A nickel(ii)-manganese(ii)-azido layered coordination polymer showing a three-dimensional ferrimagnetic order at 35 K.

The work in this report describes the synthesis, characterization, crystal structure and magnetic properties of a two-dimensional azido-bridged NiIIMnII heterometallic coordination polymer, [{(NiIILMnII)2(µ1,1,3-N3)2}(µ1,3-N3)2]n (1), in which the H2L Schiff base is the [2 + 1] condensation product of 3-methoxysalicylaldehyde and 1,3-diaminopropane. In 1, two bis(µ-phenoxo)-µ1,1,3-azido-NiIIMnII dinuclear units are interlinked to form a dimer-of-dinuclear moiety {NiIIMnII}2; the {NiIIMnII}2 structural units are further interlinked with each other by µ1,3-azido ligands to form a layered coordination polymer. Upon cooling, the χMT product slowly decreases from 300 K to about 100 K, then increases abruptly from 3.74 cm3 K mol-1 at 100 K to 113.2 cm3 K mol-1 at 30 K, indicating a ferrimagnetic behaviour; a three-dimensional magnetic order below 37 K was determined by the divergence in the ZFC-FC measurements and ac measurements, in which the peak temperature 35 K in the in-phase at different frequencies suggests that the Curie temperature is 35 K, whereas the out-of-phase is somewhat frequency dependent, due to the glassy magnet behaviour. The title compound is among the rare examples of metallo-organic systems having a magnetic ordering Curie temperature above 30 K. Other interesting aspects in 1 regarding magnetic properties and structural features are discussed.

Syntheses, crystal structures, magnetic properties and ESI-MS studies of a series of trinuclear CuIIMIICuII compounds (M = Cu, Ni, Co, Fe, Mn, Zn).

Six trinuclear CuIIMIICuII compounds (M = Cu, Ni, Co, Fe, Mn, Zn) derived from the Schiff base ligand, H2L (2 + 1 condensation product of salicylaldehyde and trans-1,2-diaminocyclohexane) are reported in this investigation. The composition of the metal complexes are [{CuIIL(ClO4)}2CuII(H2O)]·2H2O (1), [{CuIIL(ClO4)}{NiII(H2O)2}{CuIIL}]ClO4·CH3COCH3 (2), [{CuIIL(ClO4)}{CoII(CH3COCH3)(H2O)}{CuIIL(CH3COCH3)}]ClO4 (3) and isomorphic [{CuIIL(ClO4)}2MII(CH3OH)2] (4, M = Fe; 5, M = Mn; 6, M = Zn). Two copper(ii) ions in 1-6 occupy N2O2 compartments of two L2- ligands, while the second metal ion occupies the O(phenoxo)4 site provided by the two ligands, i.e., the two metal ions in both CuIIMII pairs are diphenoxo-bridged. Positive ESI-MS of 1-6 reveals some interesting features. Variable-temperature and variable-field magnetic studies reveal moderate or weak antiferromagnetic interactions in 1-6 with the following values of magnetic exchange integrals (H = -2JS 1 S 2 type): J 1 = -136.50 cm-1 and J = 0.00 for the CuIICuIICuII compound 1; J 1 = -22.16 cm-1 and J = -1.97 cm-1 for the CuIINiIICuII compound 2; J 1 = -14.78 cm-1 and J = -1.86 cm-1 for the CuIICoIICuII compound 3; J 1 = -6.35 cm-1 and J = -1.17 cm-1 for the CuIIFeIICuII compound 4; J 1 = -6.02 cm-1 and J = -1.70 cm-1 for the CuIIMnIICuII compound 5; J = -2.25 cm-1 for the CuIIZnIICuII compound 6 (J is between two CuII in the N2O2 compartments; J 1 is between CuII and MII through a diphenoxo bridge).

Experimental and theoretical exploration of magnetic exchange interactions and single-molecule magnetic behaviour of bis(η1:η2:µ2-carboxylate)Gd/Dy systems.

The present report deals with the syntheses, crystal structures, dc/ac magnetic properties and DFT/ab initio CASSCF calculations of two isomorphous bis(η1:η2:µ2-acetate)GdIII2/DyIII2 compounds of the formula [LnIII2L2(acetate)4(MeOH)2] (1, Ln = Gd; 2, Ln = Dy), where HL is (E)-N'-(3-ethoxysalicylidene)acetohydrazide. The two lanthanide(iii) centres in each compound are symmetry-related owing to the presence of an inversion centre. Both compounds exhibit intramolecular ferromagnetic exchange interactions. The DyIII2 analogue is a single-molecule magnet (SMM) with Ueff = 52.8 cm-1 and τ0 = 1.52 × 10-6 s. DFT calculations for 1 and ab initio calculations for 2 also reveal ferromagnetic interactions. Ab initio calculations of the SMM behaviour of 2 and two other reported and structurally related compounds reveal the importance of the weak exchange interaction present between the two DyIII ions, and a relaxation mechanism has been developed to take into account the magnetic exchange interaction and to rationalize the observed difference in the Ueff values.

Syntheses, crystal structures and magnetic properties of two mixed-valence Co(iii)Co(ii) compounds derived from Schiff base ligands: field-supported single-ion-magnet behavior with easy-plane anisotropy.

Two µ-phenoxo-µ1,1-azide dinuclear CoIIICoII complexes [CoIII(N3)2L1(µ1,1-N3)CoII(N3)]·MeOH (1) and [CoIII(N3)2L2(µ1,1-N3)CoII(N3)]·MeOH (2) (HL1 and HL2 are two Schiff base ligands having N2O-N2O compartments) both possess one hexacoordinate Co(iii) and one pentacoordinate Co(ii) center. DC magnetic susceptibility and magnetization measurements show an appreciable amount of positive magnetic anisotropy (D/hc∼ 40 cm-1) that is also confirmed by ab initio CASSCF calculations. AC susceptibility measurements of 1 reveal that it exhibits a slow magnetic relaxation with two relaxation channels. The external magnetic field supports the low-frequency (LF) channel that escapes on heating more progressively than the high-frequency (HF) branch. The relaxation time is as slow as τ = 255 ms at T = 1.9 K and BDC = 0.6 T, where the LF mole fraction is 69%. The complex 2 also displays similar field-supported slow magnetic relaxation with two relaxation channels.

Syntheses, crystal structures and steady state and time-resolved fluorescence properties of a PET based macrocycle and its dinuclear ZnII/CdII/HgII complexes.

The work in the present investigation reports the syntheses, crystal structures, ESI-MS (positive) and steady state and time resolved photophysical properties of a tetraaminodiphenol macrocyclic ligand H2L (saturated analogue of a tetraiminodiphenol macrocycle obtained on 2 + 2 condensation of 4-ethyl-2,6-diformylphenol and 2,2-dimethyl-1,3-diaminopropane) and its three dinuclear d10 metal ion (ZnII, CdII and HgII) complexes having compositions [ZnLCl2]·2CH3OH (1), [CdL(µ-H2O)(H2O)2](NO3)2·4H2O (2) and [HgLCl2] (3). H2L is colorless and weakly fluorescent, Cd compound 2 is colorless and more weakly fluorescent, Zn compound 1 is colorless and highly fluorescent and Hg compound 3 is yellow and nonemissive. The order of the radiative rate constant (Kr), obtained from time-resolved studies, corroborates the order of quantum yields, obtained from steady state studies: 1 (φ = 0.12; Kr = 116.6 × 106 s-1) ≫ H2L (φ = 0.005; Kr = 7.726 × 106 s-1) > Cd compound 2 (φ = 0.0014; Kr = 0.675 × 106 s-1). Spectrophotometric and steady state/time-resolved spectrofluorimetric titrations of H2L with ZnII, CdII and HgII have been performed. The relative fluorescence efficiencies of H2L, H2L + various single metal ions (ZnII, CdII, HgII, CuII, NiII, CoII, FeII, MnII) and H2L + ZnII + another metal ion (metal ion competition study) have been studied. Relative fluorescence efficiency can be well rationalized in terms of photoinduced electron transfer (PET), perturbation of PET by metal coordination (chelation enhanced fluorescence, CHEF), heavy metal ion effect (spin-orbit coupling) and fluorescence quenching mechanism. It has been established from comparative fluorescence spectra of 4-ethylphenol, H2L and 1 that H2L can be reasonably considered as a PET species in which the fluorophore is 4-ethylphenol. The binding constants, as determined from titration experiments, qualitatively corroborate the results of metal ion competition studies. The modulation of the absorption spectra and color of the H2L-HgII solution in the presence of various diamagnetic metal ions has been explored. Significant aspects of structures and spectroscopic properties have been discussed.

Bis-phenoxido and bis-acetato bridged heteronuclear {Co(III)Dy(III)} single molecule magnets with two slow relaxation branches.

Two bis-µ-phenoxido-bis-µ-acetato heterobimetallic {Co(III)Dy(III)} complexes and , formulated as [Co(III)Dy(III)L(µ-OAc)2(NO3)2] derived from the comparable hexadentate Schiff bases N,N'-ethylenebis(3-ethoxysalicylaldimine) and N,N'-ethylenebis(3-methoxysalicylaldimine) were synthesized and X-ray structure analysis confirms their nearly identical structures. These are the first examples of bis(µ-phenoxido)-bis(µ-carboxylato) {Co(III)Dy(III)} systems. The AC susceptibility measurements show that both complexes exhibit a field-induced slow magnetic relaxation with two relaxation branches. While the high-frequency process spans the usual range of the relaxation time for analogous single molecule magnets (τ0 ∼ 10(-7) s), the low-frequency branch is as slow as τ ∼ 0.1 s at T = 1.9 K and B = 0.2 T.

Model Compounds for Iron Proteins. Structures and Magnetic, Spectroscopic, and Redox Properties of Fe(III)M(II) and [Co(III)Fe(III)](2)O Complexes with (&mgr;-Carboxylato)bis(&mgr;-phenoxo)dimetalate and (&mgr;-Oxo)diiron(III) Cores.

A series of heterobimetallic complexes of the type [Fe(III)M(II)L(&mgr;-OAc)(OAc)(H(2)O)](ClO(4)).nH(2)O (2-5) and [{Fe(III)Co(III)L(&mgr;-OAc)(OAc)}(2)(&mgr;-O)](ClO(4))(2).3H(2)O (6) where H(2)L is a tetraaminodiphenol macrocyclic ligand and M(II) = Zn(2), Ni(3), Co(4), and Mn(5) have been synthesized and characterized. The (1)H NMR spectrum of 6 exhibits all the resonances between 1 and 12 ppm. The IR and UV-vis spectra of 2-5 indicate that in all the cases the metal ions have similar coordination environments. A disordered crystal structure determined for 3 reveals the presence of a (&mgr;-acetate)bis(&mgr;-phenoxide)-Ni(II)Fe(III) core, in which the two metal ions have 6-fold coordination geometry and each have two amino nitrogens and two phenolate oxygens as the in-plane donors; aside from the axial bridging acetate, the sixth coordination site of nickel(II) is occupied by the unidentate acetate and that of iron(III) by a water molecule. The crystal structure determination of 6 shows that the two heterobinuclear Co(III)Fe(III) units are bound by an Fe-O-Fe linkage. 6 crystallizes in the orthorhombic space group Ibca with a = 17.577(4) Å, b = 27.282(7) Å, c = 28.647(6) Å, and Z = 8. The two iron(III) centers in 6 are strongly antiferromagnetically coupled, J = -100 cm(-1) (H = -2JS(1).S(2)), whereas the other two S(1) = S(2) = (5)/(2) systems, viz. [Fe(2)(III)(HL)(2)(&mgr;-OH)(2)](ClO(4))(2) (1) and the Fe(III)Mn(II) complex (5), exhibit weak antiferromagnetic exchange coupling with J = -4.5 cm(-1) (1) and -1.8 cm(-1) (5). The Fe(III)Ni(II) (3) and Fe(III)Co(II) (4) systems, however, exhibit weak ferromagnetic behavior with J = 1.7 cm(-1) (3) and 4.2 cm(-1) (4). The iron(III) center in 2-5 exhibits quasi-reversible redox behavior between -0.44 and -0.48 V vs Ag/AgCl associated with reduction to iron(II). The oxidation of cobalt(II) in 4 occurs quasi-reversibly at 0.74 V, while both nickel(II) and manganese(II) in 3 and 5 undergo irreversible oxidation at 0.85 V. The electrochemical reduction of 6 leads to the generation of 4.