Synthesis of some novel CoII and CoIII complexes by tribochemical reactions using KI with some derivatives of thiosemicarbazide complexes derived from Girard's T and P

The starting Co(II) complexes of the general formulae, [Co(L1)2]Cl4.4H2O, [Co(L1)Cl2]Cl (L1=N-([(allyl amino)thioxomethyl]hydrazinocarbonylmethyl) trimethylammonium chloride; ATHTC), [Co(L2)Cl]Cl.2H2O.(1/2)EtOH (L2=N-([(ethylamine)thioxomethyl]hydrazinocarbonylmethyl)trimethylammonium chloride; ETHTC) and [Co(L3)Cl2]Cl.2EtOH (L3=N-([(phenylaminomethyl)thioxomethyl]hydrazinocarbonylmethyl)pyridinium chloride; PTHPC), were synthesized by the conventional chemical methods. Tribochemical reactions of the above mentioned CoII complexes obtained by chemical methods with KI afford novel CoII and CoIII complexes with the general formulae [Co(L1')I3.(1/2)EtOH]I, [Co2(L1')I4]I.EtOH, [Co(L2')I2.(3/2)EtOH]I, [Co2(L2')I4(OEt)2(H2O)2]I.(1/2)EtOH and [Co(L3')I2.H2O]I.3H2O. The ligands (L1', L2' and L3') formed by tribochemical reactions are quite similar to these of L1, L2 and L3, except that the ionizable chloride ions in case of L1, L2 and L3 are substituted by iodide ions in (L1', L2' and L3'). The isolated solid CoII and CoIII complexes have been characterized by elemental analyses, conductivities, spectral (IR, UV-vis, 1H NMR) and magnetic measurements. The IR spectra of the starting CoII complexes indicate that both L1 and L3 behave in bidentate manner coordinating via the carbonyl oxygen and NH2 groups, but L2 behaves as a tridentate fashion coordinating via the carbonyl oxygen, azomethine (C=N2) and SH groups with displacement of a hydrogen atom from the latter group. On the other hand, the IR spectra of the iodide CoII and CoIII complexes, synthesized by tribochemical reactions, suggest that L1' behaves only in a bidentate fashion via NH1 and CS groups. L2' behaves either as bidentate ligand through NH1 and CSH with deprotonation from the latter group or as a tetradentate ligand towards two cobalt ions via OH, C=N2, C=N1 and C-SH with displacement of a hydrogen atom from the latter group. Moreover, L3' behaves in a tetradentate ligand, toward two cobalt ions via the carbonyl oxygen, NH2, NH1 and CSH with displacements of a hydrogen atom from the latter group. The spectral and magnetic results suggest a tetrahedral geometry for all CoII complexes prepared by conventional chemical methods. The diamagnetic nature for three of the five iodide complexes, prepared by tribochemical reactions, suggests the oxidation of CoII to CoIII ion and the existence of low spin-octahedral geometry around the CoIII ion. Finally, the results of the rest of the iodide CoII complexes suggest either tetrahedral and/or high-spin octahedral geometry.     

Synthesis, Crystal Structure and Magnetic Properties of a New 3D Cobalt Vanadate

A new cobalt vanadate compound 1 [Co^Ⅱ(H2O)2V2^VO6] has been hydrothermally synthesized and characterized by the elemental analyses and the single crystal X-ray diffraction analysis. Compound 1 crystallizes in the orthorhombic system, space group Pinna, with a=0.55646, b=1.06900, c=1.18452 nm, and Z=4. The magnetic susceptibility of the cobalt vanadate has been measured and indicates possible antiferromagnetic coupling between adjacent cobalt (Ⅱ) (0.5432—0.5697 nm) through bond or space.     

A mixed-valence polyoxovanadate(III,IV) cluster with a calixarene cap exhibiting ferromagnetic V(III)-V(IV) interactions

A series of compounds (cat)[V6O6(OCH3)8(calix)(CH3OH)] was obtained under anaerobic conditions and solvothermal reaction of VOSO4 with p-tert-butylcalix[4]arene (calix) in methanol using different types of bases (Et4NOH, NH4OH, pyridine, Et3N). All compounds contain the same polyoxo(alkoxo)hexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) exhibiting a mixed valence {VIIIVIV5O19} core with the so-called Lindqvist structure coordinated to a calix[4]arene macrocycle and cocrystallizing with the conjugated acid of the base (cat = Et4N+, NH4(+), pyridinium, Et3NH+) involved in the synthesis process. The structures have been fully established from X-ray diffraction on single crystals and the mixed valence state has been confirmed by bond valence sum calculations. The magnetic behavior of all compounds are the same because of the polyalkoxohexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) and have been interpreted by DFT calculations. Thus the V(III)...V(IV) interactions are found to be weakly ferromagnetic (<5.5 cm(-1)) while the V(IV)...V(IV) are antiferromagnetic (-17.6; -67.6 cm(-1)). The set of the coupling exchange parameters allows a good agreement with the magnetic experimental data.     

Co[HO2C(CH2)3NH(CH2PO3H)2]2: a new canted antiferromagnet

A new cobalt(II) carboxylate-phosphonate, namely, Co[HO2C(CH2)3NH(CH2PO3H)2]2, with a layered architecture has been synthesized by hydrothermal reactions. The Co(II) ion in the title compound is octahedrally coordinated by six phosphonate oxygen atoms from four carboxylate phosphonate ligands. Neighboring CoO6 octahedra are interconnected by phosphonate groups into a 2D layer with a 4,4-net topology. Adjacent layers are further cross-linked via hydrogen bonds between the noncoordinate carboxylate groups and noncoordinate phosphonate oxygens. The ac and dc magnetic susceptibility and magnetization measurements indicate that Co[HO2C(CH2) 3NH(CH2PO3H)2]2 is a canted antiferromagnet with T(c) = 8.75 K.     

Characterization of the chloranilate(*3-) pi radical as a strong spin-coupling bridging ligand

Dinuclear [(TPA)Co(II)(CA2-)Co(II)(TPA)](BF4)2.2MeOH (1) [TPA = tris(2-pyridylmethyl)amine] and [(TPA)CoII(CA*3-)CoII(TPA)](BF4).2Et2O (2) with a bridging chloranilate radical ligand formed by reduction of 1 are crystallographically and magnetically characterized. 1 has shown a weak antiferromagnetic coupling within the Co(II) dimer [J/kB = -0.65 K (-0.45 cm(-1))], while 2 has a 2 orders of magnitude stronger antiferromagnetic interaction between the Co(II) ion and a radical [J/kB = -75 K (52 cm(-1))].     

Acetonitrile hydration and ethyl acetate hydrolysis by pyrazolate-bridged cobalt(II) dimers containing hydrogen-bond donors

The preparation of new CoII-mu-OH-CoII dimers with the binucleating ligands 3,5-bis{bis[(N'-R-ureaylato)-N-ethyl]aminomethyl}-1H-pyrazolate ([H4PRbuam]5-, R=tBu, iPr) is described. The molecular structure of the isopropyl derivative reveals that each CoII center has a trigonal-bipyramidial coordination geometry, with a Co...Co separation of 3.5857(5) A. Structural and spectroscopic studies show that there are four hydrogen-bond (H-bond) donors near the CoII-micro-OH-CoII moiety; however, they are too far away to be form intramolecular H-bonds with the bridging hydroxo ligand. Treating [CoII2H4PRbuam(micro-OH)]2- with acetonitrile led to the formation of bridging acetamidato complexes, [CoII2H4PRbuam(micro-1,3-OC(NH)CH3)]2-; in addition, these CoII-micro-OH-CoII dimers hydrolyze ethyl acetate to form CoII complexes with bridging acetato ligands. The CoII-1,3-micro-X'-CoII complexes (X'=OAc-, [OC(NH)CH3]-) were prepared independently by reacting [CoII2H3PRbuam]2- with acetamide or [CoII2H4PRbuam]- with acetate. X-ray diffraction studies show that the orientation of the acetate ligand within the H-bonding cavity depends on the size of the R substituent appended from the urea groups. The tetradentate ligand 3-{bis[(N'-tert-butylureaylato)-N-ethyl]aminomethyl}-5-tert-butyl-1H-pyrazolato ([H2PtBuuam]3-) was also developed and its CoII-OH complex prepared. In the crystalline state, [CoIIH2PtBuuam(OH)]2- contains two intramolecular H-bonds between the urea groups of [H2PtBuuam]3- and the terminal hydroxo ligand. [nPr4N]2[CoIIH2PtBuuam(OH)] does not hydrate acetonitrile or hydrolyze ethyl acetate. In contrast, K2[CoIIH2PtBuuam(OH)] does react with ethyl acetate to produce KOAc; this enhanced reactivity is attributed to the presence of the K+ ions, which can possibly interact with the CoII-OH unit and ester substrate to assist in hydrolysis. However, K2[CoIIH2PtBuuam(OH)] was still unable to hydrate acetonitrile.     

The first examples of metal-mediated addition of a phosphorus imine to nitriles; the preparation and X-ray crystal structures of [PtCl4{NH=C(Et)N=PPh3}2] and [PtCl2(EtCN){NH=C(Et)N[double bond, length as m-dash]PPh3}

Imino(triphenyl)phosphorane, Ph3P=NH (1), reacts with nitrile complexes of Pt(IV) to generate hydrolytically sensitive [PtCl4{NH=C(R)N=PPh3}2](R=Me 2a, Et 2b, Ph 2c), and with the Pt(II) complex [PtCl2(EtCN)2] to give [PtCl2(EtCN){NH=C(Et)N=PPh3}](3) and [PtCl2{NH=C(Et)N=PPh3}2](4); X-ray crystallography performed upon (2b) and (3) confirms the presence of an imine/nitrile addition ligand bound by the terminal nitrogen.     

Pop-the-cork strategy in synthetic utilization of imines: stabilization by complexation and activation via liberation of the ligated species

Treatment of trans-[PtCl(4)(RCN)(2)] (R = Me, Et) with ethanol allowed the isolation of trans-[PtCl(4)[E-NH[double bond]C(R)OEt](2)]. The latter were reduced selectively, by the ylide Ph(3)P[double bond]CHCO(2)Me, to trans-[PtCl(2)[E-NH[double bond]C(R)OEt](2)]. The complexed imino esters NH[double bond]C(R)OEt were liberated from the platinum(II) complexes by reaction with 2 equiv of 1,2-bis(diphenylphosphino)ethane (dppe) in chloroform; the cationic complex [Pt(dppe)(2)]Cl(2) precipitates almost quantitatively from the reaction mixture and can be easily separated by filtration to give a solution of NH[double bond]C(R)OEt with a known concentration of the imino ester. The imino esters efficiently couple with the coordinated nitriles in trans-[PtCl(4)(EtCN)(2)] to give, as the dominant product, [PtCl(4)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)] containing a previously unknown linkage, i.e., ligated N-(1-imino-propyl)-alkylimidic acid ethyl esters. In addition to [PtCl(4)[NH[double bond]C(Et)N[double bond]C(Et)OEt](2)], another compound was generated as the minor product, i.e., [PtCl(4)(EtCN)[NH[double bond]C(Et)N[double bond]C(Et)OEt]], which was reduced to [PtCl(2)(EtCN)[NH[double bond]C(Et)N[double bond]C(Et)OEt]], and this complex was characterized by X-ray single-crystal diffraction. The platinum(IV) complexes [PtCl(4)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)] are unstable toward hydrolysis and give EtOH and the acylamidine complexes trans-[PtCl(4)[Z-NH[double bond]C(Et)NHC(R)[double bond]O](2)], where the coordination to the Pt center results in the predominant stabilization of the imino tautomer NH[double bond]C(Et)NHC(R)[double bond]O over the other form, i.e., NH(2)C(Et)[double bond]NC(R)[double bond]O, which is the major one for free acylamidines. The structures of trans-[PtCl(4)[Z-NH[double bond]C(Et)NHC(R)[double bond]O](2)] (R = Me, Et) were determined by X-ray studies. The complexes [PtCl(4)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)] were reduced to the appropriate platinum(II) compounds [PtCl(2)[NH[double bond]C(Et)N[double bond]C(R)OEt](2)], which, similarly to the appropriate Pt(IV) compounds, rapidly hydrolyze to yield the acylamidine complexes [PtCl(2)[NH[double bond]C(Et)NHC(R)[double bond]O](2)] and EtOH. The latter acylamidine compounds were also prepared by an alternative route upon reduction of the corresponding platinum(IV) complexes. Besides the first observation of the platinum(IV)-mediated nitrile-imine ester integration, this work demonstrates that the application of metal complexes gives new opportunities for the generation of a great variety of imines (sometimes unreachable in pure organic chemistry) in metal-mediated conversions of organonitriles, the "storage" of imino species in the complexed form, and their synthetic utilization after liberation.     

A novel helical double-layered cobalt(II)-organic framework with tetranuclear [Co4(mu3-OH)2] clusters linked by an unsymmetrical pyridylbenzoate ligand

A novel cobalt(II)-organic framework, [Co2(OH)(3,4-PBC)3]n (I), has been acquired by the reaction of CoO with an unsymmetrical pyridylbenzoate ligand, 3-pyrid-4-ylbenzoic acid (3,4-PBC). Single-crystal X-ray diffraction studies reveal that it is comprised of [CoII4(mu3-OH)2] clusters linked by the unsymmetrical ligand 3,4-PBC, forming a novel helical double-layered metal-organic architecture. A significant overall antiferromagnetic behavior has been observed for this compound.     

Platinum(IV)-mediated nitrile-sulfimide coupling: a route to heterodiazadienes

Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.     

Probing single-chain magnets in a family of linear chain compounds constructed by magnetically anisotropic metal-ions and cyclohexane-1,2-dicarboxylate analogues

Five new metal-carboxylate chain-based laminated compounds, namely, infinity2[FeII(e,e-trans-1,2-chdc)] (3) (1,2-chdc = cyclohexane-1,2-dicarboxylate), infinity2[NiII(mu-OH2)(e,a-cis-1,2-chdc)] (4), infinity2[CoII(mu-OH2)(1,2-chedc)] (5) (1,2-chedc = cyclohex-1-ene-1,2-dicarboxylate), infinity2[Co5II(mu3-OH)2(OH2)2(1,2-chedc)4] (6), and infinity2[CoII(4-Me-1,2-chdc)] (7) (4-Me-1,2-chdc = trans-4-methylcyclohexane-1,2-dicarboxylate) have been hydrothermally synthesized. In these series of magnetic chain-based compounds, 3 and 7 have the same dimeric paddle-wheel M(II)-carboxylate chain as the previously reported compound, infinity2[CoII(trans-1,2-chdc)] (2). However, compound 3 does not behave as a single-chain magnet (SCM) but simply an alternating ferro-antiferro magnetic chain. Compound 4 has the cis conformation of 1,2-chdc ligand, which leads to a uniform aqua-carboxylate-bridged Ni(II) chain. Such a Ni-O chain exhibits strong antiferromagnetic interactions, leading to a diamagnetic ground state. Compound 5 features a corner-sharing triangular chain, or delta-chain, which is part of a Kagom lattice. However, 5 does not exhibit a spin-frustrated effect but simply spin competition. Compound 6 has a unique pentanuclear CoII cluster, which is further connected by the syn-anti carboxylate into a chain structure. Compound 6 exhibits antiferromagnetic interactions among the Co(II) ions, and no SCM behavior is observed. These results might indicate that the dimeric paddle-wheel Co(II)-carboxylate chain is essential in obtaining SCM behavior in this family of compounds. Although 2 and 7 have very similar SCM behavior, alternating current magnetic studies show that 7 has a higher energy barrier than that of 2. Such behavior is probably caused by the larger anisotropic energy barrier in 7.     

Hydrothermal Synthesis and Structure Characterization of Open-framework Cobalt-tungsten Phosphate[H3NCH2CH2NH3]3[Co3W4P4O28]

A new three-dimensional open-framework cobalt(Ⅱ)-tungsten(Ⅵ) phosphate,[H3NCH2CH2NH3]3·[Co3W4P4O28](1) has been synthesized from the reaction of CoCl2·6H2O,WO3,H3PO4,ethylenediamine and H2O.The title compound was fully characterized by infrared spectroscopy,elemental analysis,magnetic properties,thermogravimetric analysis,XPS and single-crystal X-ray diffraction.The compound crystallized in a tetragonal space group I4(1)/a with a=1.7118(4) nm,c=1.0773(2) nm,V =3.1568(11) nm3,Z =4.     

Reaction with dioxygen of a Cu(I) complex of 1-benzyl-[3-(2'-pyridyl)]pyrazole triggers ethyl acetate hydrolysis: acetato-/pyrazolato-, dihydroxo- and diacetato-bridged Cu(II) complexes

A copper(I) compound [(L2)Cu(MeCN)2][ClO4] (1) containing a new bidentate N-donor ligand L2, 1-benzyl-[3-(2'-pyridyl)]pyrazole, derived from the condensation of HL1 [HL1 = 3-(2-pyridyl)pyrazole] and benzyl chloride, has been synthesized. Structural analysis reveals that in the copper(I) centre is coordinated by a pyridine and a pyrazole nitrogen from L2 and two MeCN molecules, providing a distorted tetrahedral geometry. Reaction of with dioxygen in N,N'-dimethylformamide (dmf) at 25 degrees C and subsequent workup with MeCO2Et afforded an acetato-/pyrazolato-bridged polymeric copper(II) compound [(mu-L1)Cu(mu-O2CMe)]n (2). Notably, the deprotonated form of HL(1) and MeCO2- have originated from debenzylation of L2 and hydrolysis of MeCO2Et, respectively. The structural analysis of reveals a near-planar {Cu2(mu-L1)2}2+ core unit in which two adjacent Cu(II) ions are bridged by the deprotonated N,N-bidentate pyridylpyrazole units of two L1 and each such {Cu2(mu-L1)2}2+ unit is bridged by MeCO2- in a monodentate bridging mode [Cu...Cu separations (A): 3.9232(4) pyrazolate bridge; 3.3418(4) acetate bridge], providing a polymeric network. Careful oxygenation of in MeCN led to the isolation of a dihydroxo-bridged dicopper(II) compound [{(L2)Cu(mu-OH)(OClO3)}2] (3). Interestingly, complex brings about hydrolysis of MeCO2Et under mild conditions (dmf, ca. 60 degrees C), generating a bis-mu-1,3-acetato-bridged dicopper(II) complex, [{(L2)Cu(dmf)(mu-O2CMe)}2][ClO4]2.dmf.0.5MeCO2H (4). Compounds and have {Cu2(mu-OH)2}2+ [Cu...Cu separation of 2.8474(9) A] and {Cu2(mu-O2CMe)2}2+ cores [Cu...Cu separation: 3.0988(26) and 3.0792(29) A (two independent molecules in the asymmetric unit)] in which each Cu(II) centre is terminally coordinated by L2. A rationale has been provided for the observed debenzylation of L2 and hydrolysis of MeCO(2)Et. The intramolecular magnetic coupling between the Cu(II) (S = 1/2) ions was found to be ferromagnetic (2J = 82 cm(-1)) in the case of , but antiferromagnetic for (2J = -158 cm(-1)) and (2J = -96 cm(-1)). Absorption and EPR spectroscopic properties of the copper(II) compounds have also been investigated.     

Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [CoⅡ(2,2'-bipy)2(H2O)]2[SiWVI12O40]·2H2O

A Keggin-type tungstosilicate compound [CoII(2,2'-bipy)2(H2O)]2[SiWVI12O40]·2H2O1 (bipy = bipyridine) was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C4H40Co2N8O44SiW12) crystallizes in the triclinic system, space group P1 with a = 10.4979(6), b = 13.3946(7), c = 13.5756(8) (A°), α= 70.0769(18), β= 68.910(3), y = 74.186(4)°,V =1649.84(16) (A°)3, M, = 3688.95, Z =1, Dc= 3.713 mg.m-3,μ= 21.432 mm-1, F(000) = 1644, S =1.058, the final R = 0.0511 and wR = 0.1023 for 6523 observed reflections (I> 2σ(I)). Compound 1 consists of two coordinated cation fragments [CoII(2,2'-bipy)2(H2O)]2+, one normal Keggin polyanion unit [SiWVI12O40]4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photo-luminescence property in the solid state at room temperature.     

Supramolecular incorporation of fullerenes on gold surfaces: comparison of C60 incorporation by self-assembled monolayers of different calix[n]arene (n = 4, 6, 8) derivatives

[reaction: see text] Two new calix[6]arene derivatives 3 and 4 in a 1,4-anti conformation and one calix[8]arene derivative 5 were synthesized. SAMs of calix[n]arene (n = 4, 6, 8) derivatives 1-5 were formed on gold bead electrodes. Cyclic voltammetry with Ru(NH3)6(3+/2+) as a redox probe, together with impedance spectroscopy and reductive desorption, indicates that SAMs of 5 have a higher coverage than those of 3 and 4 due to the presence of hydrogen bonding and possibly its conformation. Noncovalent immobilization of C60 on gold surfaces was achieved with SAMs of calix[8]arene derivative 5 but not with those of 1-4.     

Cobalt(II) citrate cubane single-molecule magnet

An investigation of the magnetic properties of the cobalt(II) citrate cubane [C(NH 2) 3] 8{Co 4(cit) 4}.4H 2O reveals that the cluster is a new cobalt(II) single-molecule magnet, with an energy barrier to reorientation of the magnetization, Delta E/ k B = 21 K, and tau 0 = 8 x 10 (-7) s. The compound displays distinct, frequency-dependent peaks in the out-of-phase (chi') component of the ac magnetic susceptibility and magnetization versus field hysteresis loops that are temperature and sweep rate dependent. The hysteresis loops collapse at zero field due to very fast quantum tunneling of the magnetization (QTM).     

Archetypical modeling and amphiphilic behavior of cobalt(II)-containing soft-materials with asymmetric tridentate ligands

The stabilization of a bivalent oxidation state in cobalt complexes of phenolate-based asymmetric tridentate ligands with iodo and bromo substituents is studied. The complexes [CoII(LIA)2].2CH3OH (1) and [CoII(LBrA)2].CH3OH (2) were characterized by means of several spectroscopic and spectrometric techniques. The molecular structure of 1 was determined by diffractometric analysis and reveals the cobalt(II) ion in a distorted-octahedral geometry. The centrosymmetric metal ion adopts a local D2h symmetry and is surrounded by facially coordinated ligands. Equivalent donor sets in both ligands are trans to each other, and DFT calculations suggest that the fac-trans configuration is favored by a small margin when compared to the fac-cis isomers. Both DFT calculations and EPR spectroscopy agree with a high-spin S=3/2 electronic configuration given by [ag1, b1g1, ag1, b2g2, b3g2]. This oxidation state was indirectly observed by the lack of a ppiphenolate-->dsigma*cobalt(III) charge-transfer band, which is found between 430 and 470 nm for similar cobalt(III) species. On the basis of the geometrical preferences and the oxidation state of archetypical 1 and 2, two metallosurfactants [CoII(LI-ODA)2] (3) and [CoII(LI-NOBA)2].CH2Cl2 (4) were obtained. The redox chemistry of 1-4 is marked by metal- and ligand-centered activity with several follow up processes and film formation on the electrode. Both metallosurfactants exhibit amphiphilic properties and organization, as shown by compression isotherms and Brewster angle microscopy but exhibit dissimilar collapse mechanisms; whereas 3 collapses at constant pressure, 4 exhibits a constant-area collapse. Langmuir-Blodgett films are readily obtained and were characterized by equilibrium contact angle and atomic force microscopy.     

Phosphorus-based p-tert-butylcalix[5]arene ligands

New calix[5]arene trivalent phosphorus derivatives have been synthesized which should be excellent ligands with which to study and control the interaction of a ligand atom with a metal. The larger cavity of the calix[5]arene (compared to calix[4]arene) provides a good balance between constraint and flexibility. Treatment of p-tert-butylcalix[5]arene with 2 equiv of either tris(dimethylamino)phosphine or dichlorophenylphosphine inserts two RP moieties into the calix[5]arene framework to give calix[5](PR)2(OH) (1, R = Me2N; 2, R = Ph). Further treatment of 1 with 4 equiv of HCl gives calix[5](PCl)2(OH) (3). Heating a solution of the monophosphorus compound calix[5](PNMe2)(OH)3 (4) releases dimethylamine to yield both monomeric calix[5](P)(OH)2 (6) and dimeric [calix[5](P)(OH)2](2) (7), the latter having a tubelike geometry. X-ray crystallographic studies confirm the structures and show that 1 and 2 have approximate cone conformations while 3 has an approximate 1,2-alternate conformation. The orientations of the phosphorus lone pairs and oxygen atoms in all derivatives provide a framework for both soft and hard ligand interactions within the calix[5]arene.     

Reduction of (imine)Pt(IV) to (imine)Pt(II) complexes with carbonyl-stabilized phosphorus ylides

A novel method is reported for generation of the difficult-to-obtain (imine)Pt(II) compounds that involves reduction of the corresponding readily available Pt(IV)-based imines by carbonyl-stabilized phosphorus ylides, Ph3P=CHCO2R, in nonaqueous media. The reaction between neutral (imino)Pt(IV) compounds [PtCl4[NH=C(Me)ON=CR1R2]2] [R1R2 = Me2, (CH2)4, (CH2)5, (Me)C(Me)=NOH], [PtCl4[NH=C(Me)ONR2]2] (R = Me, Et, CH2Ph), (R1 = H; R2 = Ph or C6H4Me; R3 = Me) as well as anionic-type platinum(IV) complexes (Ph3PCH2Ph)[PtCl5[NH=C(Me)ON=CR2]] [R2 = Me2, (CH2)4, (CH2)5] and 1 equiv of Ph3P=CHCO2R (R = Me, Et) proceeds under mild conditions (ca. 4 h, room temperature) to give selectively the platinum(II) products (in good to excellent isolated yields) without further reduction of the platinum center. All thus prepared compounds (excluding previously described Delta4-1,2,4-oxadiazoline complexes) were characterized by elemental analyses, FAB mass spectrometry, IR and 1H, 13C[1H], 31P[1H] and 195Pt NMR spectroscopies, and X-ray single-crystal diffractometry, the latter for [PtCl2[NH=C(Me)ON=CMe2]2] [crystal system tetragonal, space group P4(2)/n (No. 86), a = b = 10.5050(10) A, c = 15.916(3) A] and (Ph3PCH2CO2Me)[PtCl3(NCMe)] [crystal system orthorhombic, space group Pna2(1) (No. 33), a = 19.661(7) A, b = 12.486(4) A, c = 10.149(3) A]. The reaction is also extended to a variety of other Pt(II)/Pt(IV) couples, and the ylides Ph3P=CHCO2R are introduced as mild and selective reducing agents of wide applicability for the conversion of Pt(IV) to Pt(II) species in nonaqueous media, a route that is especially useful in the case of compounds that cannot be prepared directly from Pt(II) precursors, and for the generation of systematic series of Pt(II)/Pt(IV) complexes for biological studies.     

Synthesis,Characterization, and Properties of Supported Tungstozincate Bridged by Co（Ⅱ） Complex Fragment

[Co^11（phen）3]2[{（ZnW12O40）Co^11（phen）2（H2O）}2Co^11（trien）2（NaH2O）2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31°, V=9.239 nm^3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{（ZnW12O40）Co（phen）2（H2O）}2Co（C6H18N4）2·（NaH2O）2]^4- in which each supported Keggin anion [（ZnW12O40Co^11（phen）2（H2O）]^4- acts as a ligand to coordinate to central bridging Co^2＋ ion via a terminal oxygen atom. Hydrogen bonds are responsible for the construction of 3D architecture of the compound. The compound is paramagnetic with a weak antiferromagnetic interaction（0=-46.796 K）.