Ferromagnetism in malonato-bridged copper(II) complexes. Synthesis,crystal structures,and magnetic properties of [[Cu(H2O)3][Cu(mal)2(H2O)]]n and [[Cu(H2O)4]2[Cu(mal)2(H2O)]][Cu(mal)2(H2O)2][[Cu(H2O)4][Cu(mal)2(H2O)2][(H2mal = malonic acid)

Three malonato-bridged copper(II) complexes of the formulas [[Cu(H2O)3][Cu(C3H2O4)2(H2O)]]n (1), [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]] [Cu(C3H2O4)2(H2O)2][[Cu(H2O)4][Cu(C3H2O4)2(H2O)2]] (2), and [Cu(H2O)4][Cu(C3H2O4)2(H2O)2] (3) (C3H2O4 = malonate dianion) have been prepared, and the structures of the two former have been solved by X-ray diffraction methods. The structure of compound 3 was already known. Complex 1 crystallizes in the orthorhombic space group Pcab, Z = 8, with unit cell parameters of a = 10.339(1) A, b = 13.222(2) A, and c = 17.394(4) A. Complex 2 crystallizes in the monoclinic space group P2/c, Z = 4, with unit cell parameters of a = 21.100(4) A, b = 21.088(4) A, c = 14.007(2) A, and beta = 115.93(2) degrees. Complex 1 is a chain compound with a regular alternation of aquabis(malonato)copper(II) and triaquacopper(II) units developing along the z axis. The aquabis(malonato)copper(II) unit acts as a bridging ligand through two slightly different trans-carboxylato groups exhibiting an anti-syn coordination mode. The four carboxylate oxygens, in the basal plane, and the one water molecule, in the apical position, describe a distorted square pyramid around Cu1, whereas the same metal surroundings are observed around Cu2 but with three water molecules and one carboxylate oxygen building the equatorial plane and a carboxylate oxygen from another malonato filling the apical site. Complex 2 is made up of discrete mono-, di-, and trinuclear copper(II) complexes of the formulas [Cu(C3H2O4)2(H2O)2]2-, [[Cu(H2O)4] [Cu(C3H2O4)2(H2O)2]], and [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]]2+, respectively, which coexist in a single crystal. The copper environment in the mononuclear unit is that of an elongated octahedron with four carboxylate oxygens building the equatorial plane and two water molecules assuming the axial positions. The neutral dinuclear unit contains two types of copper atoms, one that is six-coordinated, as in the mononuclear entity, and another that is distorted square pyramidal with four water molecules building the basal plane and a carboxylate oxygen in the apical position. The overall structure of this dinuclear entity is nearly identical to that of compound 3. Finally, the cationic trimer consists of an aquabis(malonato)copper(II) complex that acts as a bismonodentate ligand through two cis-carboxylato groups (anti-syn coordination mode) toward two tetraaqua-copper(II) terminal units. The environment of the copper atoms is distorted square pyramidal with four carboxylate oxygens (four water molecules) building the basal plane of the central (terminal) copper atom and a water molecule (a carboxylate oxygen) filling the axial position. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-290 K. Overall, ferromagnetic behavior is observed in the three cases: two weak, alternating intrachain ferromagnetic interactions (J = 3.0 cm-1 and alpha J = 1.9 cm-1 with H = -J sigma i[S2i.S2i-1 + alpha S2i.S2i+1]) occur in 1, whereas the magnetic behavior of 2 is the sum of a magnetically isolated spin doublet and ferromagnetically coupled di- (J3 = 1.8 cm-1 from the magnetic study of the model complex 3) and trinuclear (J = 1.2 cm-1 with H = -J (S1.S2 + S1.S3) copper(II) units. The exchange pathway that accounts for the ferromagnetic coupling, through an anti-syn carboxylato bridge, is discussed in the light of the available magneto-structural data.     

[Mn(H2O)4(NCS)2](18-冠-6)的分子和晶体结构

报导了[Mn(H2O)4(NCS)2](18-冠-6)单晶的X射线结构分析.它的晶体正交晶系.锰(II)与两个硫氰酸根,四个水分子配合形成顺式八面体的配位分子,并通过其中的水分子与18-冠-6以氢键结合.     

Synthesis,crystal structure,and magnetic properties of K4Mn3(HPO4)4(H2PO4)2

A new layered compound, K₄Mn₃(HPO₄)₄(H₂PO₄)₂ (1), has been synthesized under hydrothermal conditions. It crystallizes in the monoclinic space group P2₁/n with a = 8.874(2) Å, b = 6.554(1) Å, c = 18.075(4) Å, and β = 93.39(3)°. The structure consists of zigzag [Mn₃O₁₄]_n chains of edge-sharing MnO₆ octahedrons and MnO₇ pentagonal bi-pyramids, which form layers of formula [Mn₃(HPO₄)₄(H₂PO₄)₂]^4? in the ab plane via H₂PO₄ and HPO₄ units with vertex-sharing. Potassium ions lie between these layers. Magnetic measurements indicate Curie–Weiss behavior above 6 K for 1. A Heisenberg model, with alternating exchange interactions J₁J₁J₂… within the chain and exchange interactions J₃J₃… between the chains, is proposed to describe the magnetic behavior.     

Tetranuclear manganese(II) complexes of sulfonylcalix[4]arene macrocycles: synthesis, structure, spectroscopic and magnetic properties

Two tetranuclear manganese(II) complexes {K(+)[Mn(4)(ThiaSO(2))(2)(OH)](-)} (1) and {K(+)[Mn(4)(ThiaSO(2))(2)(F)](-)} (2) have been synthesized under solvothermal conditions in methanol with p-tert-butylsulfonylcalix[4]arene (ThiaSO(2)). For both complexes, the structure has been established from single-crystal X-ray diffraction. The two complexes are best described as manganese squares sandwiched between two thiacalixarene macrocycles. In both complexes, in the center of the square formed by the four manganese(II) atoms, the unexpected presence of μ(4)-OH(-) or μ(4)-F(-) gives a negative charge to the cluster. The two tetranuclear complexes exhibit strong orange luminescence behavior resulting from the symbiosis between the ThiaSO(2) and the Mn(2+). Despite similar chemical formulation, (1) and (2) present difference in emission intensity and lifetime τ.     

[Mn(phen)2(H2O)2]2[Cr(OX)3][HOCH2CH2O].4H2O的合成、晶体结构及性质

在二甲亚砜(DMSO)中, 以MnCl2.2H2O和K3[Cr(Ox)3].3H2O为原料, 合成了离子型配合物[Mn(phen)2(H2O)2]2[Cr(OX)3][HOCH2CH2O].4H2O。晶体结构测定表明, 该晶体属单斜晶系, P2/c空间群。晶体学参数: a=1.0602(3),b=1.3515(3), c=2.1508(3)nm, β=102.57(2)°, V=3.008(1)nm^3, Z=2,Dc=1.49g/cm^3, F(000)=1392。最后的偏差因子R=0.067。测定了化合物的UV-Vis-NIR, IR, XPS, ESR光谱和变温磁化率, 讨论了相应的性质。     

Syntheses, crystal structures, and spectroscopic and magnetic properties of [Mn2III(H2L1)(Cl4Cat)4.2H2O] and [Mn2III(H2L2)(Cl4Cat)4.2CH3CN.2H2O]infinity: temperature-dependent valence tautomerism in solution

The synthesis, X-ray data, and electronic structures of two manganese(III) 1D polymers ligated by tetrachlorocatechol, [Mn(2)(III)(H(2)L(1))(Cl(4)Cat)(4).2H(2)O](infinity) (1) and [Mn(2)(III)(H(2)L(2))(Cl(4)Cat)(4).2CH(3)CN.2H(2)O](infinity) (2), are reported. The electronic structures of the complexes have been determined by UV-vis-near-IR, IR, electron paramagnetic resonance (EPR), and magnetic susceptibility measurements. Both 1 and 2 are air stable in the solid state and in solution, unlike most of the previously reported o-quinone-chelated transition-metal complexes. Electronic spectroscopy exhibits a strong near-IR band near 1900 nm for both, suggesting the presence of a mixed-valence semiquinone-catecholate oxidation state of the catechol ligands, Mn(2)(III)(Cl(4)Cat)(2)(Cl(4)SQ)(2), together with the pure catecholate forms. The presence of this isomer was further supported by EPR and magnetic susceptibility measurements. The complexes undergo intramolecular electron transfer (valence tautomerism) upon an increase of the temperature involving the equilibrium Mn(2)(III)(Cl(4)Cat)(2)(Cl(4)SQ)(2) <==> Mn(2)(II)(Cl(4)SQ)(4). This phenomenon is reversible and is studied in solution using UV-vis-near-IR spectroscopy.     

Synthesis,crystal structure and activity for H2O2 disproportionation of a binuclear manganese(III) complex [(tol)Mn(bbml)2Mn(tol)](ClO4)2

The title binuclear Mn₂(III) complex was synthesized through the reaction of 2-[bis(2-benzimidazolylmethyl)amino]ethanol (Hbbml), Mn(DMSO)₆(ClO₄)₃ and o-toluic acid (Htol). X-ray structure analysis shows that the two Mn(III) atoms are bridged by the oxygen atoms of the two bbml ligands, forming a bis(μ-alkoxo)dimanganese core. Electrospray mass spectrometry (ES-MS) experiments shows that the complex cation may easily lose one or two tol⁻ ligands leaving an unoccupied coordination site, which would favor the coordination and activation of H₂O₂. Furthermore, its catalytic activity for the disproportionation of H₂O₂ and the effect of added heterocyclic base were also investigated. The complex has some similarities to manganese catalase in structure and activity.     

Cyano-bridged Mn(III)3M(III) (M(III) = Fe, Cr) complexes: synthesis, structure, and magnetic properties

Two cyano-bridged tetranuclear complexes composed of Mn(III) salen (salen = N,N'-ethylene bis(salicylideneiminate)) and hexacyanometalate(III) (M = Fe, Cr) in a stoichiometry of 3:1 have been selectively synthesized using {NH2(n-C12H25)2}3[M(III)(CN)6] (M(III) = Fe, Cr) starting materials: [{Mn(salen)(EtOH)}3{M(CN)6}] (M = Fe, 1; Cr, 2). Compounds 1 and 2 are isostructural with a T-shaped structure, in which [M(CN)6]3- assumes a meridional-tridentate building block to bind three [Mn(salen)(EtOH)]+ units. The strong frequency dependence and observation of hysteresis on the field dependence of the magnetization indicate that 1 is a single-molecule magnet.     

Synthesis, nuclear, and magnetic structures and magnetic properties of [Mn3(OH)2(SO4)2(H2O)2

[Mn(3)(OH)(2)(SO(4))(2)(H(2)O)(2)] and its deuterated analogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single-crystal X-ray analysis and Rietveld analysis of neutron powder-diffraction data, consists of a 3D network of chains of edge-sharing Mn(1)O(6), running along the c axis, connected by the apices of Mn(2)O(6) and SO(4) units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long-range ordering (LRO) and short-range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54 degrees towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn(3) trimer, the LRO is achieved by antiparallel alignment of the four symmetry-related trimers within the magnetic unit cell. A spin-flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.     

Synthesis,crystal structure and properties of manganese(II) hexafluoroacetylacetonates Mn(hfa)2(H2O)2 and KMn(hfa)3

Two manganese(II) hexafluoroacetylacetonate complexes, dihydrate, the Mn(hfa)₂(H₂O)₂ (1), and the bimetallic KMn(hfa)₃ (2) have been synthesized and characterized by X-ray single crystal structure analysis. They have a molecular structure and a polymeric structure, respectively. The high stability of 2 allowed sublimation without decomposition. It was then used as a precursor for MOCVD of fluoroperovskite, KMnF₃.     

The search for 3d-4f single-molecule magnets: synthesis, structure and magnetic properties of a [Mn(III)2Dy(III)2] cluster

Tetranuclear [Mn(III)2Ln(III)2] complexes formed using tripodal ligands display frequency dependent out-of-phase ac susceptibility signals and temperature and sweep rate dependent hysteresis loops.     

A new inorganic-organic hybrid iron(III) arsenate: (C2H10N2)[Fe(HAsO4)2(H2AsO4)](H2O). Hydrothermal synthesis, crystal structure, and spectroscopic and magnetic properties

A new iron(III) arsenate templated by ethylenediamine, (C2H10N2) [Fe(HAsO4)2(H2AsO4)](H2O), has been prepared by hydrothermal synthesis. The unit-cell parameters are a = 8.705(3) A, b = 16.106(4) A, c = 4.763(1) A, beta = 90.63(3) degrees; monoclinic, P2(1) with Z = 2. The compound exhibits a chain structure along the c-axis with the ethylenediammonium cations as counterion. The chains show isolated FeO6 octahedra with two HAsO4 and one H2AsO4 tetrahedra per FeO6 octahedron. The ESR spectrum at 5.0 K is isotropic with a g-value of 2.0, which remains practically unchanged at room temperature. Magnetic measurements indicate the presence of antiferromagnetic interactions. A value of -0.835 K for the J-exchange parameter has been calculated by fitting the magnetic data to a model for antiferromagnetic chains of spin S = 5/2.     

[Mn(phen)3](ClO4)2(H2O)·0.5(azpy)的合成和晶体结构

锰在生物体系的新陈代谢过程中有重要作用。锰有机配合物的研究成为生物无机化学研究领域的一个热点[1]。本文报道用高氯酸锰、1,10 邻菲咯啉和4,4 偶氮联吡啶[2 4]合成的锰配合物[Mn(phen)3](ClO4)2(H2O)·0 5(azpy)的晶体结构。1　实验部分1 1　Mn(Ⅱ)配合物的合成将0 0724g(0 2mmol)Mn(ClO4)2·6H2O溶于8mL水,缓慢加入含有0 1190g(0 6mmol)1,10 邻菲咯啉(phen)和0 0277g(0 15mmol)4,4′ 偶氮联吡啶(azpy)的15mL甲醇溶液,搅拌0 5h,室温下静置,一周后得[Mn(phen)3](ClO4)2(H2O)·0 5(azpy)晶体。元素分析(计算值)/%:C54 19(54 …     

Synthesis,crystal structure and magnetic properties of [Mn(LH)2(H2O)2] n with a two-dimensional layered structure and three-dimensional hydrogen bonding network

A new manganese polymer [Mn(LH)₂(H₂O)₂] _n (LH₂ = iminodiacetic acid) (1) has been prepared and structurally and magnetically characterized. The polymer has a two-dimensional (2D) layered structure with the unique Mn atom on an inversion center, surrounded by six oxygen atoms. In each layer, all iminodiacetic acid entities are coordinated to Mn atoms in a bridging/bidentate mode, thus linking the [Mn(LH)₂(H₂O)₂] monomeric units together to form a 2D layered polymer. Hydrogen bonding is responsible for an extended three-dimensional network. Analysis of variable-temperature magnetic susceptibility data (2–300) K shows that the polymer displays weak antiferromagnetic exchange interaction with a coupling constant, J = –0.28 cm^–1.     

A heteropentanuclear oxalato-bridged [Re(IV)(4)Gd(III)] complex: synthesis, crystal structure and magnetic properties

The compound (NBu(4))(5)[Gd(III){Re(IV)Br(4)(μ-ox)}(4)(H(2)O)]·H(2)O (1), with intramolecular antiferromagnetic coupling, is the first Re(iv) system incorporating a 4f ion.     

First MnIII complexes with tetradentate (N2O2) Schiff bases and tricyanomethanide: synthesis,crystal structure,and magnetic properties

The first Mn^III complexes with Schiff bases and tricyanomethanide-anion were synthesized: [Mn(salen)C(CN)₃(H₂O)] (1), [Mn(5-Brsalen)C(CN)₃(H₂O)] (2), [Mn(salpn)C(CN)₃(H₂O)] (3), [Mn(3-MeOsalen)C(CN)₃(H₂O)] (4), [Mn(5-Brsalen)(MeOH)(H₂O)][C(CN)₃] (5), and [Mn(3-MeOsalpn)(H₂O)₂][C(CN)₃] (6), where SalenH₂ is N,N′-bis(salicylidene)ethylenediamine, 5-BrsalenH₂ is N,N′-bis(5-bromosalicylidene)ethylenediamine, SalpnH₂ is N,N′-bis-(salicylidene)-1,3-diaminopropane, 3-MeOsalenH₂ is N,N′-bis(3-methoxysalicylidene)-ethylenediamine, 3-MeOsalpnH₂ — N,N′-bis(3-methoxysalicylidene)-1,3-diaminopropane. The tricyanomethanide anion in complexes 1–4 acts as a the terminal ligand, whereas in complexes 5 and 6 tricyanomethanide is not coordinated by Mn^III and acts as an out-of-sphere counterion. The structures of complexes 1–4 are characterized by the formation of dimers due to hydrogen bonds between the water molecules and oxygen atoms of the Schiff bases. The Mn...Mn distances inside the dimers are 4.69–5.41 Å. Complex 6 has a zigzag chain structure consisting of the [Mn(3-MeOsalpn)(H₂O)₂]⁺ cations bound by double bridging aqua ligands. The study of the magnetic properties of complexes 1, 3, 4, and 6 showed the existence of antiferromagnetic interactions between the Mn^III ions through the system of hydrogen bonds.     

Crystal structure of tetraphenylarsonium aquatetracyanonitridorhenate(V), (AsPh4)2 [ReN(H2O)(CN)4]·5H2O

The crystal structure of (AsPh₄)₂[ReN(H₂O)(CN)₄]·5H₂O has been determined from three-dimensional X-ray diffraction data. The yellow crystals are monoclinic, space group P2₁/n with cell dimensionsa=15.482(1),b=19.950(2),c=16.999(1)? and β=101.69(6)^o,Z=4,D _expt=1.48(1)g cm⁻³ andD _calc=1.52g cm⁻³. The anisotropic refinement of 7858 observed reflections converged toR=0.055. The [ReN(H₂O)(CN)₄]²⁻ ion has a distorted octahedral geometry. Bond distances: Re≡N=1.639(8), Re−OH₂=2.496(7) and Re−C_(av)=2.11(1) ?. The rhenium atom is displaced by 0.35 ? out of the plane formed by the four carbon atoms of the cyano ligands towards the terminal nitrido ligand. TMC 2479     

Solvothermal synthesis,crystal structure and properties of Mn2(tren)3[Mo2O2S6]2·1.3H2O exhibiting the new polymeric [Mn2(tren)3] n 4+ chain

The novel oxothiomolybdate Mn₂(tren)₃[Mo₂O₂S₆]₂·1.3H₂O [tren = tris(2-aminoethyl)amine], synthesized under solvothermal conditions, consists of one-dimensional novel [Mn₂(tren)₃] _n ⁴⁺ chains and discrete [Mo₂O₂S₆]^2– anions. There are two crystallographically independent chains and four [Mo₂O₂S₆]^2– anions in the asymmetric unit. Each Mn atom in the cationic chains is sixfold coordinated by N atoms of the chelating tren molecules. Two of the four crystallographically independent Mn atoms are tridentately coordinated by two tren molecules, whereas the other two are coordinated tetradentately by one tren molecule and monodentately by the remaining primary amino groups from the tren molecules that act as tridentate ligands. The tren ligand bonding modes lead to the formation of the polymeric [Mn₂(tren)₃] _n ⁴⁺ chain. One of the four Mn atoms is in the unusual trigonal prismatic coordination state with six surrounding N atoms.     

Novel K/Mn phosphate hydrates,K2Mn3(H2O)2[P2O7]2 and KMn(H2O)2[Al2(PO4)3]: hydrothermal synthesis and crystal chemistry

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K₂Mn₃(H₂O)₂[P₂O₇]₂, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H₂O)₂[Al₂(PO₄)₃], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X‐ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: A₂M₃(H₂O)₂[P₂O₇]₂, where A = K, NH₄, Rb or Na and M = Mn, Fe, Co or Ni, and AM²⁺(H₂O)₂[M³⁺₂(PO₄)₃], where A = Cs, Rb, K, NH₄ or (H₃O); M²⁺ = Mn, Fe, Co or Ni; and M³⁺ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit‐cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO₂)₂(PO₄)₂]_∞ layers, with a cationic topology similar to the Si/Al‐topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.