Reporting a unique example of electronic bistability observed in the form of valence tautomerism with a copper(II) helicate of a redox-active nitrogenous heterocyclic ligand.

Valence tautomeric compounds involving nondixolene-type ligands are rare. The triple-helicate copper(II) complex [Cu(II)(2)(L)(3)](ClO(4))(4)·3CH(3)CN (1) containing a redox-active N-heterocyclic ligand (L) has been prepared and displays VT equilibrium in solution, as established by electronic spectroscopy, electron paramagnetic resonance spectroscopy, and cyclic and differential pulse voltammetry carried out at variable temperatures. The process involves intramolecular transfer of an electron from one of the L ligands to a copper(II) center, leading to the oxidation of L to an L(•+) radical with concomitant reduction of the Cu(II) center to Cu(I), as shown by the equilibrium [Cu(II)Cu(I)L(•+)L(2)](4+) ⇄ [Cu(II)(2)L(3)](4+).

Single crystal-to-single crystal irreversible transformation from a discrete vanadium(V)-alcoholate to an aldehydic-vanadium(IV) oligomer.

An unprecedented single crystal-to-single crystal transformation occurs when a binuclear oxovanadium(V) compound [V(V)(2)O(2)(L)(2)] 1 involving 2,6-bis(hydroxymethyl)-p-cresol (H(3)L) as a bridging ligand is exposed simultaneously to white light and aerial oxygen to generate an oligomeric compound [V(IV)(2)O(2)(L*)(2)] 2 (H(2)L* is 3-hydroxymethyl-5-methylsalicylaldehyde). Each vanadium(V) center in 1 is reduced to vanadium(IV) in 2 at the expense of a two-electron alcohol-to-aldehyde oxidation in the coordinated ligand. The additional electron being released is possibly consumed by molecular oxygen to generate hydrogen peroxide.

Vanadium-induced nucleophilic IPSO substitutions in a coordinated tetrachlorosemiquinone ring: formation of the chloranilate anion as a bridging ligand.

In basic media, the coordinated semiquinone radical in the spin-coupled [(bipy)ClV(IV)O(TCSQ)] 1 (HTCSQ = tetrachlorosemiquinone) undergoes nucleophilic ipso substitution (OH- for Cl-) to generate the chloranilate anion (CA(2-)) that bridges the vanadium(IV) centers, forming a binuclear compound [(bipy)ClV(IV)O(CA)OV(IV)Cl(bipy)] 2.

Tetra-, tri-, and mononuclear manganese(II/III) complexes of a phenol-based N2O2 capping ligand: use of carboxylates as ancillary ligands in tuning the nuclearity of the complexes.

Manganese(II/III) complexes of a phenol-based tetradentate ligand L(2-) [H(2)L = N,N'-dimethyl-N,N'-bis(2-hydroxy-3,5-dimethylbenzyl)-ethylenediamine], namely, [Mn(4)(L)(2)(PhCOO)(6)] (1), [Mn(3)(L)(2)(CH(3)CH(2)COO)(2)(OMe)(2)].H(2)O (2), and [Mn(L){(CH(3))(3)CCOO}(CH(3)OH)].CH(3)OH (3), have been synthesized. The basicity and steric congestion provided by the carboxylate moiety used as an ancillary ligand have profound influence on tuning the nuclearity of these compounds. Results of X-ray crystallography, electronic spectroscopy, and variable-temperature (1.8-300 K) magnetic measurements have been used to characterize these compounds. Complex 1 has a very interesting centrosymmetric structure that involves two crystallographically equivalent binuclear [Mn(II)-Mn(III)] units, connected together by a pair of syn-anti bridging benzoates to generate a "dimer of dimers" structural motif. Compound 2 with propionate as the ancillary ligand, on the other hand, has a nearly linear Mn(III)-Mn(II)-Mn(III) core with antiferromagnetically coupled (J = -0.13 cm(-1)) metal centers. Compound 1 has an S(T) = 9 spin ground state with ferromagneticlly coupled metal centers (J(wb)= 2.8(1) and J(bb) = 0.09(2) cm(-1)) that failed to function as a single molecule magnet due to the presence of low-lying excited states with smaller spin values and a weak magnetic anisotropy. The electron paramagnetic resonance spectrum of 1 in the frozen solution (12 K) displays two signals in the g = 2 and g = 4 regions, each split into six lines due to (55)Mn (I = 5/2) superhyperfine couplings. The use of bulky pivalate as a replacement for benzoate provides enough steric bulk to generate a mononuclear species [Mn(L){(CH(3))(3)CCOO}(CH(3)OH)].CH(3)OH (3). The lone manganese(III) center in this compound has an octahedral geometry, completed by the tetradentate ligand L(2-) together with an axially coordinated methanol molecule and a monodentate pivalate. The latter two are connected by a hydrogen bond, thus stabilizing the monodentate carboxylate moiety. Redox behaviors (CV) of 1 and 3 are grossly similar, each undergoing a quasi-reversible reduction process at E(1/2) = -0.03 and -0.11 V, respectively, versus a Ag/AgCl reference.

Hetero-bimetallic complexes involving vanadium(V) and rhenium(VII) centers, connected by unsupported mu-oxido bridge: synthesis, characterization, and redox study.

Heterobimetallic complexes of a vanadium(V) and rhenium(VII) combination connected by a mu-oxido bridge [LVO(mu-O)ReO 3].H 2O [H 2L = N, N'-ethylene bis(salicylideneimine) (H 2salen) and its methoxy derivative] ( 1, 2) are reported. The compounds have been prepared by a single-pot synthesis in which the precursor [V (IV)OL] complexes are allowed to be oxidized aerially in the presence of added perrhenate. The oxidized [V (V)OL] (+) species accommodate the ReO 4 (-) anion in their vacant coordination site, trans to the terminal oxido group, providing the complexes 1 and 2. The later generates a binuclear oxovanadium(V) compound [H 2en][(TBC)VO(mu-TBC) 2OV(TBC)].5H 2O ( 3) when treated with tetrabromocatechol. Single crystal X-ray diffraction analysis and (1)H NMR spectroscopy have been used to establish their identities. In compound 2, the Re(1)-O(11)-V(1) bridge angle is barely linear [170.2(3) degrees ] with a Re...V separation of 3.9647(9) A. The redox behavior of 1 and 2 are quite interesting, each undergoing two reductions both in the positive potential range at E 1/2 = 0.59 (process I) and E 1/2 = 0.16 V (process II) versus Ag/AgCl reference (corresponding potentials are 0.59 and 0.18 V for 2). Process I has a single-electron stoichiometry involving the [VO(salen)] part of the complexes as established by combined coulometry-Electron Paramagnetic Resonance (EPR) experiments which provide an eight-line isotropic EPR pattern at room temperature ( = 1.967; = 87 x 10 (-4) cm (-1)), characteristic of an unpaired electron being coupled to a vanadium nuclear spin ( (51)V, I = 7/2). The almost linear V-O-Re bridge in 1 and 2 allows this unpaired electron to interact effectively with the neighboring Re nuclear spin, leading to familiar " two-line pattern" superhyperfine coupling ( A ( (185,187)Re) = 20.7 x 10 (-4) cm (-1)). Process II, on the other hand, is based on a Re(VII/VI) electron transfer as confirmed by differential pulse and normal pulse voltammetric experiments.

Tetra- and dinuclear nickel(II)-vanadium(IV/V) heterometal complexes of a phenol-based N2O2 ligand: synthesis, structures, and magnetic and redox properties.

The tetra- and binuclear heterometallic complexes of nickel(II)-vanadium(IV/V) combinations involving a phenol-based primary ligand, viz., N,N'-dimethyl-N,N'-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine (H2L1), are reported in this work. Carboxylates and beta-diketonates have been used as ancillary ligands to obtain the tetranuclear complexes [Ni(II)(2)V(V)(2)(RCOO)(2)(L(1))(2)O(4)] (R = Ph, 1; R = Me(3)C, 2) and the binuclear types [(beta-diket)Ni(II)L(1)V(IV)O(beta-diket)] (3 and 4), respectively. X-ray crystallography shows that the tetranuclear complexes are constructed about an unprecedented heterometallic eight-membered Ni(2)V(2)O(4) core in which the (L(1))(2)- ligands are bound to the Ni center in a N(2)O(2) mode and simultaneously bridge a V atom via the phenoxide O atoms. The cis-N(2)O(4) coordination geometry for Ni is completed by an O atom derived from the bridging carboxylate ligand and an oxo O atom. The latter two atoms, along with a terminal oxide group, complete the O5 square-pyramidal coordination geometry for V. Each of the dinuclear compounds, [(acac)Ni(II)L(1)V(IV)O(acac)] (3) and [(dbm)Ni(II)L(1)V(IV)O(dbm)] (4) [Hdbm = dibenzoylmethane], also features a tetradentate (L(1))(2)- ligand, Ni in an octahedral cis-N(2)O(4) coordination geometry, and V in an O(5) square-pyramidal geometry. In 3 and 4, the bridges between the Ni and V atoms are provided by the (L(1))(2)- ligand. The Ni...V separations in the structures lie in the narrow range of 2.9222(4) A (3) to 2.9637(5) A (4). The paramagnetic Ni centers (S = 1) in 1 and 2 are widely separated (Ni...Ni separations are 5.423 and 5.403 A) by the double V(V)O(4) bridge that leads to weak antiferromagnetic interactions (J = -3.6 and -3.9 cm-1) and thus an ST = 0 ground state for these systems. In 3 and 4, the interactions between paramagnetic centers (Ni(II) and V(IV)) are also antiferromagnetic (J = -8.9 and -10.0 cm-1), leading to an S(T) = 1/2 ground state. Compound 4 undergoes two one-electron redox processes at E(1/2) = +0.66 and -1.34 V vs Ag/AgCl reference due to a V(IV/V) oxidation and a Ni(II)/I reduction, respectively, as indicated by cyclic and differential pulse voltammetry.

Reporting a new class of divanadium(V) compounds connected by an unsupported hydroxo bridge.

Dinuclear oxovanadium(V) compounds [LV(V)O(mu-OH)OV (V)L](PF6) [H2L = N,N'-tert-ethylene bis(salicylideneimine) (H 2Salen) and its derivatives] ( 1- 3) have been obtained by aerial oxidation of V (IV)OL precursors in THF in the presence of added NH 4PF 6. The oxidized vanadium(V) probably extracts an OH (-) ligand from the residual moisture in the solvent and is retained as an unsupported hydroxo-bridge between the metal centers of these compounds as confirmed by single-crystal X-ray diffraction analyses. The molecules of 1- 3 have centrosymmetric structures with each vanadium center having a distorted octahedral geometry. The bridging OH (-) group is located trans to the terminal VO t bond. The latter exerts strong trans labilizing influence to set the participating vanadium centers apart by about 4.1 A. These separations are by far the largest (e.g., V...V#, 4.131 A in 1) among all binuclear compounds containing an unsupported hydroxo bridge reported to date. The complexes retain their identity also in solution as established by (1)H NMR spectroscopy. Electrochemically, the behaviors of 1-3 are quite interesting as studied by cyclic voltammetry in acetonitrile, each undergoing three (except 3) nearly reversible metal-based reductions, all in the positive potential range (e.g., at E (1/2) = 0.57, 0.39, and 0.04 V versus Ag/AgCl reference for 1) as indicated by steady state voltammetry. The electrode process at 0.39 V appears to involve a single-step two-electron transfer as revealed from the normal and differential pulse voltammetric data and probably includes a combination of V(V)-V(IV) <--> V(III)-V(IV) mixed oxidation states. Compounds 1-3 thus provide a unique example of divanadium compounds in which the metal centers are linked by an unsupported hydroxo-bridge.

Coordination asymmetry in divanadium(V) compounds containing a V2O3 core: synthesis, characterization, and redox properties.

A general protocol for the synthesis of micro-oxo divanadium(V) compounds [LOV(micro-O)VO(Salen)] (1-5) incorporating coordination asymmetry has been developed for the first time. One of the vanadium centers in these compounds has an octahedral environment, completed by tetradentate Salen ligand, while the remaining center has square pyramidal geometry, made up of tridentate biprotic Schiff-base ligands (L2-) with ONO (1-3) and ONS (4, 5) type donor combinations. Single crystal X-ray diffraction analysis, ESI-MS, and NMR (both 1H and 51V) spectroscopy have been used extensively to establish their identities. The V(1)-O(6)-V(2) bridge angle in these compounds, save 3, lie in a narrow range (166.20(9)-157.79(16) degrees) with the V2O3 core having a rare type of twist-angular structure, somewhat intermediate between the regular anti-linear and the syn-angular modes. For 3, however, the bridge angle is sufficiently smaller 117.92(8) degrees that it forces the V2O3 core to adopt an anti-angular geometry. The V(1)...V(2) separations in these molecules (3.7921(7)-3.3084(6) A) are by far the largest compared to their peers containing a V2O3 core. The molecules retain the binuclear structures also in solution as confirmed by NMR spectroscopy. Their redox behaviors appear quite interesting, each undergoing a one-electron reduction in the positive potential range (E1/2, 0.42-0.45 V vs Ag/AgCl) to generate a trapped-valence mixed-oxidation products [LVVO-(micro-O)-OVIV(salen)]1-, confirmed by combined coulometry-EPR experiments. The bent V-O-V bridge in these molecules probably prevents the symmetry-constrained vanadium d xy orbitals, containing the unpaired electron, to overlap effectively via the ppi orbitals of the bridging oxygen atom, thus accounting for the trapped-valence situation in this case.

Targeted synthesis of mu-oxo divanadium(V) compounds with asymmetry in coordination environments.

Isovalent mu-oxo divanadium(V) compounds [L1VO(mu-O)VO(salen)] (1) and its bromo derivative [L2VO(mu-O)VO(salen)].CH3CN (2) (both H2L1 and H2L2 are tridentate dithiocarbazate-based ONS ligands) with ligands providing donor set and coordination number asymmetry in tandem have been synthesized for the first time; confirmations in favor of these unsymmetrical molecular structures have come from single-crystal X-ray diffraction analysis, as well as from NMR (both 1H and 51V) spectroscopy.

Bi- and trinuclear copper(II) complexes of a sterically constrained phenol-based tetradentate ligand: syntheses, structures, and magnetic studies.

Copper(II) complexes (1-3) of a sterically constrained phenol-based tetradentate N(2)O(2) ligand 1,4-bis(2-hydroxy-3,5-dimethylbenzyl)piperazine (H(2)L) have been reported. The associated anions of the copper(II) ion precursors have profound influence on the stoichiometry of the products. Thus, with perchlorate ion, the product is a binuclear compound [Cu(2)L(2)] (1), while with coordinating anions viz. Cl(-) and N(3)(-), the products [Cu(3)L(2)Cl(2)(H(2)O)].1/2H(2)L (2) and [Cu(3)L(2)(N(3))(2)(CH(3)OH)].4H(2)O (3) have triangulo trinuclear composition. The syntheses, X-ray structures, and spectroscopic and magnetic properties of these complexes are described. Compound 1 has a noncentrosymmetric structure with a rectangular Cu(2)(OPh)(2) core. It appears to be a rare example of a phenolato-bridged Cu(II) dimer exhibiting ferromagnetic interactions (J = 0.93 cm(-)(1)), a behavior in agreement with the theoretical predictions but seldom observed experimentally. In compounds 2 and 3, the copper centers are triangularly disposed, and the molecules have a shape much like that of a butterfly. The terminal copper centers Cu(1) and Cu(2) in 2 and 3 have distorted square pyramidal geometry, connected to each other by a bridging chloro- (in 2) or azido ligand (in 3) in "end to end" fashion. The central copper center (Cu(3) in 2 and Cu in 3) in both the compounds has distorted square planar geometry. The separations between the metal centers, viz. Cu(1)...Cu(2), Cu(2)...Cu(3), and Cu(3)...Cu(1), are 4.826, 3.214, and 3.244 A, respectively, in 2. The corresponding distances in 3 are 5.590, 3.178, and 3.485 A, respectively. The overall magnetic behaviors in 2 and 3 are consistent with antiferromagnetic interactions between the spin centers. In 3, the exchange couplings between the terminal and central copper centers J(Cu(1))(-)(Cu) and J(Cu(2))(-)(Cu) appear to be equal (-234 cm(-)(1)), resulting in an S = (1)/(2) ground state at temperatures near or below 77 K.

Honeycomb nets with interpenetrating frameworks involving iminodiacetato-copper(II) blocks and bipyridine spacers: syntheses, characterization, and magnetic studies.

Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds.