Exchange interaction and spin dynamics in pentanuclear clusters, Cu3Ln2(ClCH2COO)12(H2O)8 (Ln = Nd3+, Sm3+, Pr3+)

New compounds, [Cu₃Ln₂(ClCH₂COO)₁₂(H₂O)₈]·2H₂O with Ln = Nd³⁺ (I), Sm³⁺ (II), Pr³⁺ (III), built up of pentanuclear clusters were synthesized and studied by means of X-ray analysis and electron paramagnetic resonance (EPR). X-ray data show that all compounds are isostructural and the pentanuclear clusteres may be considered as a linear system with alternating Cu(II) and Ln(III) ions: Cu(2)-L¹-Ln-L²-Cu(1)-L²-Ln-L²-Cu(2) with L¹ and L² being bridging fragments and Cu(1) and Cu(2) being structurally nonequivalent copper complexes. EPR studies demonstrate that in the temperature range of 100–293 K the signals due to only one type of the copper complexes are observed in the spectra of I–III. AtT<100 K the spectral temperature dependence is nontrivial. AtT<30 K new signals are detected in the spectra of I and II. The temperature dependence of the EPR spectra is interpreted under the assumption that the parameter of the exchange interaction Cu(2)-Ln considerably exceeds the parameter of the interaction Cu(1)-Ln. EPR spectra are calculated for the fragments of five paramagnetic centers in the frames of the model taking into account the nonequivalence of two copper complexes, short longitudinal and transverse paramagnetic relaxation times of the rare-earth ions at room temperature and the change of the relaxation rates when the temperature decreases. The results of the calculations show that it is possible to obtain information about the interactions in the system on the basis of the analysis of the temperature dependence of the EPR spectra of the central copper complex. The parameter of the isotropic part of the exchange interaction between copper and neodymium ions (for the interaction Cu(2)-Nd) is estimated as about 15 cm⁻¹. A considerable rearrangement of the spin states when the temperature changes is found for all complexes.     

The electronic structure of the uranyl ion

Polarized single crystal absorption spectra at 4·2 K are reported for CsUO₂(NO₃)₃ and NaUO₂(CH₃COO)₃. Natural and magnetic circular dichroism and Zeeman effect measurements have been made. Measurements have also been made on crystals containing U¹⁸O₂ ²⁺. In the portion of the spectrum between 21 000 and 30 000 cm^-1 seven electronic states have been identified in both CsUO₂(NO₃)₃ and NaUO₂(CH₃COO)₃. In the majority of cases the symmetry of the excited states has been assigned.     

EPR study on the chemistry and photochemistry of copper(II) dithiocarbamate mixed-ligand complexes

The thermal and photochemical reactions of the 1∶1 mixed-ligand complexes Cu(dtc)X (X=Cl^?, NO₃ ^?, ClO₄ ^?) have been studied on the ground of their EPR spectra in acetone, CCl₄/i-PrOH (1∶1), and CHCl₃/i-PrOH (1∶1) solutions. The study allows us to get some insight into the behaviour of the mixed-ligand Cu^II(dtc)X complexes with respect to the acceptor properties of halocarbons. In CCl₄/i-PrOH (1∶1) both Cu^II(dtc)⁺…NO₃ ^? and Cu^II(dtc)⁺…ClO₄ ^? undergo thermal reactions within their donor-acceptor complexes with CCl₄ to yield Cu(dtc)Cl. On the time scale of the experiment the reaction does not occur thermally in CHCl₃/i-PrOH (1∶1), but occurs photochemically in both halocarbon/i-PrOH (1∶1) systems in which Cu(dtc)Cl is further photolyzed to CuCl₂. Continuous photolysis of the title compounds in acetone simply bleaches the solution without any intermediate EPR or light absorption.     

Evaluation of exchange interaction in binuclear copper(II) chelates of amide-based cyclophanes

Temperature dependence of the electron paramagnetic resonance (EPR) spectra of binuclear Cu(II) complexes with amide-based cyclophanes, Cu₂(bis-EDTAPDN), Cu₂(bis-EDTANAP) and Cu₂(bis-EDTABPE), in 60% methanol (pH ca. 10) has been studied at a frequency of 9.43 GHz in the temperature range of 77–4.2 K; the cyclophanes are macrocyclic compounds in which four amide bonds link two ethylenediaminetetraacetate (EDTA) units and two units of the aromatic diamine 1,4-phenylenediamine (DPN), 1,5-diaminonaphthalene (NAP) or bis(4-aminophenyl) ether (BPE). Exchange integrals found from the EPR measurements are ca. 70–105 cm^?1, 22 cm^?1 andJ ≤ 0, for Cu₂(bis-EDTAPDN), Cu₂(bis-EDTANAP) and Cu₂(bis-EDTABPE), respectively; the sign ofJ is defined to be positive for antiferromagnetic interaction. The variation of exchange interactions in these compounds is related to the nature of the bridging organic groups.     

Exchange interaction at the supramolecular level. EPR investigation of two copper (II) compounds: [Cu2(acac)2(phen)2(bpe)](CIO4)2·(bpe)·CH3CN·H2O and [Cu2(acac)2(phen)2(bpp)](CIO4)2·6H2O (bpe=trans-1,2-bis(4-pyridyl)ethylene, bpp=bis(4-pyridyl)propane)

Intra- and intermolecular exchange and dipole-dipole interactions in two supramolecular compounds [Cu₂(acac)₂(phen)₂(bpe)](CIO₄)₂·(bpe)·CH₃CN·H₂O (I) and [Cu₂(acac)₂(phen)₂(bpp)]× (CIO₄)₂·6H₂O (II), which are built up of binuclear fragments through π-π stacking interactions, are investigated. The electron paramagnetic resonance (EPR) spectra of the polycrystalline samples of I and II were measured in the X-band in the temperature range of 300–4.2 K, and in the Q-band atT=300 and 4.2 K. The EPR spectra were interpreted as being due to weakly interacting dimer fragments. Triplet and singlet states of dimer fragments arise from a larger interactionJS ₁ S ₂ between two nearest copper complexes of two neighboring binuclear fragments. The theoretical analysis of the EPR spectrum of the polycrystalline sample for weakly interacting triplet states is carried out. The influence of the weak interaction between triplet states with value ofJ′ is considered in the model of the frequency exchange. A special attention is focused on the presence of the additional signal due to the exchange merging in some orientations where theJ′ value exceeds the fine structure parameters of the spectrum. The analysis of the conditions for the detection of the additional signal and of the influence of this signal on the form of the EPR spectrum allows us to estimate the value of the exchange interactionJ′=o.025±0.005 cm^?1 for compounds I and II and anisotropic part of exchange interaction between two nearest copper complexes asJ _zz =?0.02 cm^?1,J _xx.yy =0.01 cm^?1 for compound I.     

Exchange interaction and Jahn—Teller correlations in novel tetranuclear supramolecular Cu(II) grid complexes: an ESR study

Novel tetranuclear Cu(II) complexes in which four Cu(II) ions are arranged in a square planar fashion by four bis(bipyridyl)pyrimidine ligands were investigated by X and Q band ESR in the temperature range 4.2-300 K. The ESR spectra of this grid-like structure were well simulated as rising from triplet species. Analysis of their intensities allowed the spectra to be assigned to the first excited triplet state, and revealed intramolecular antiferromagnetic coupling of the Cu(II) spins. The isotropic exchange interaction J was determined as ?47 K and reducing to about ?5 K on functionalizing the bridging pyrimidine ring at the 2-position by methyl or phenyl. For comparison an ESR investigation was also carried out on the mononuclear analogue Cu(II)—(terpyridine)₂ complexes with substituted terpyridine ligands at the 5′ and 5″ position. Depending on the substitutent, the spectra exhibit a static or dynamic Jahn—Teller effect at room temperature. The temperature dependence of their g-values is examined by a modified Silver—Getz model which includes cooperative Jahn—Teller interactions. There is evidence that both an anisotropic spin exchange contribution to D = 0.0159 cm^?1 and a coupled (static) Jahn—Teller effect are responsible for efficient coupling between the four Cu(II) ions in the grid complexes with non-substituted pyrimidine bridges.     

Spectroscopic and E. P. R Studies of the Crystal and Molecular Structure of Cu(2-Benzoylpyridine)2(NO3)2.H2O

Abstract

Solid Cu(2-Benzoylpyridine)₂(NO₃)₂ has been studied by UV-Vis, IR, and EPR (X-band, Q-band) techniques. Monoclinic crystal symmetry was determined with two molecules per unit cell. Copper (II) is coordinated by two benzoylpyridine ligands and a single NO₃ group in the chromophore CuN₂O₃ of distorted trigonal bypiramidal stereochemistry. Exchange coupling values were determined from EPR spectra as |J| = 0.0026(2) cm^?1 between magnetically nonequivalent copper (II) sites, and |J| < O.3 cm^?1 between equivalent sites.

Results are discussed by a comparison with Cu(II)-benzoyl-pyridine complexes coordinated with azide N₃ ^? anions.     

Caltrop particles synthesized by photochemical reaction induced by X‐ray radiolysis

X‐ray radiolysis of a Cu(CH₃COO)₂ solution was observed to produce caltrop‐shaped particles of cupric oxide (CuO, Cu₂O), which were characterized using high‐resolution scanning electron microscopy and micro‐Raman spectrometry. X‐ray irradiation from a synchrotron source drove the room‐temperature synthesis of submicrometer‐ and micrometer‐scale cupric oxide caltrop particles from an aqueous Cu(CH₃COO)₂ solution spiked with ethanol. The size of the caltrop particles depended on the ratio of ethanol in the stock solution and the surface of the substrate. The results indicated that there were several synthetic routes to obtain caltrop particles, each associated with electron donation. The technique of X‐ray irradiation enables the rapid synthesis of caltrop cupric oxide particles compared with conventional synthetic methods.     

Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR,optical and magnetic susceptibility measurements

Single-crystal variable temperature EPR, optical and polycrystalline magnetic susceptibility studies have been made on a novel six-coordinate Ag(II) complex. Temperature dependent EPR studies on pure single crystals of this compound reveal that dynamic Jahn-Teller distortion operates above 230 K, between 230 K and 120K static Jahn-Teller distortion sets in and below 110 K there is evidence of exchange interaction. Crystal g values were obtained by least-squares fitting with the data obtained from the orientation dependent EPR spectra of the undiluted single crystal of this complex at 300 K and 77 K. From an optical study the Jahn-Teller stabilization energy is found to be ～2250cm^?1. Comparison of Abs_max values for other silver(II) compounds enables us to conclude that the formal geometry of this complex is a tetragonally distorted octahedral. Infrared spectra of this complex were also recorded over a wide range of temperature. Magnetic susceptibility measurements over a wide range of temperature on the powder sample of this compound reveal that the complex is antiferromagnetically coupled in the temperature range 5–40 K with 2J = 0.906cm^?1, and above 40K it is ferromagnetically coupled with 2J = +7.4cm^?1. The effective magnetic moment (μ_eff) of this complex has been compared with that of a series of other silver(II) complexes available in the literature. Finally, the spectral and magnetic data of this complex have been compared with those of a corresponding isostructural and isomorphous copper(II) complex.     

A study of the temperature dependence of the rate constant for the reaction of O<Subscript>2</Subscript> with surface alkoxy radicals

A method for studying the reactions of surface alkoxy radicals with O₂ at temperatures of 230 to 300 K is described. Alkoxy radicals were generated directly in the cavity of an EPR spectrometer. Surface organic radicals, prepared from paraffin wax ((CH₃)₂(CH₂) _n , n = 16–20), were applied to Aerosil particles from a solution in heptane. The Aerosil sample was placed in the cavity of the EPR spectrometer in a cylindrical cup with a central hole for pumping out gases and exposed to H atoms. In this way, it is possible observe a steady increase in the EPR signal from the surface radicals. To measure the rate constant at tropospheric temperatures, the reaction tube was placed in a Teflon jacket, through which cool nitrogen vapor was pumped. The temperature in the reactor was varied from 230 to 300 K. The recorded EPR spectra belong to the (RO) _s radical. After obtaining a stable EPR signal from the surface radicals, treatment with H atoms was stopped, additional flow of O₂ was introduced ([O₂] = 10¹⁴–10¹⁶ cm⁻³), and the reaction of O₂ with the surface organic radicals was studied by monitoring the EPR signal decay. The temperature dependence of the rate constant for the (RO) _s + O₂ → HO₂ + ketone was obtained within T = 230–300 K. The extrapolation of the data to real tropospheric conditions ([O₂] = 10¹⁸ cm⁻³) was performed.     

EPR studies on exchange interactions in pairs of Jahn-Teller ions in Cu : Zn(pyO)6(ClO4)2

Semi-dilute 10% ⁶³Cu : Zn(pyO)₆(ClO₄)₂ [pyO = C₅H₅NO, pyridine-N-oxide] has been studied by EPR. Spectra of pairs of Cu(pyO)²⁺₆ ions are observed below the transition from dynamic to static Jahn-Teller distortion. Most of these pairs are antiferrodistortively oriented. They exhibit only the type of exchange which corresponds to the interchain interaction J′ in the pure Cu compound. From the Q-band AB type of spectrum it was found that |J′|/k = 0.041 K. An estimate of the zero- point spin reduction could be derived (～36%).     

EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn²⁺ and Cu²⁺ ions doped calcium cadmium acetate hexahydrate (CaCd(CH₃COO)₄·6H₂O) have been reported. The investigation has been carried out in the temperature range between room temperature (～ 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH₃ groups which become frozen at ～ 128 K. The incorporation of Cu²⁺ and Mn²⁺ probes at Ca²⁺ and Cd²⁺ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca²⁺ and Cd²⁺ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.     

Structure and magnetic properties of a new single-molecule magnet [Mn11Fe1O12 (CH3COO)16(H2O)4].2CH3COOH.4H2O

A new single-molecule magnet [Mn₁₁Fe₁O₁₂ (CH₃COO)₁₆(H₂O)₄]?2CH₃COOH?4H₂O (Mn₁₁Fe₁) has been synthesized.The structure has been studied by the single crystal x-ray diffraction. The difference of Jahn--Teller distortion between Fe³⁺ and Mn³⁺ ion reveals that Fe³⁺ ion substitutes for Mn³⁺ ion on the Mn(3) sites in the Mn₁₂ skeleton. The temperature dependence of the magnetization gives a blocking temperature T_B=1.9K for Mn₁₁Fe₁. Based on the magnetization process analysis of the crystal at T=2K, we suggest that Mn₁₁Fe₁ has the ground state with a total spin S= 11/2.     

Pressure-Broadened Linewidth Measurements in the ν2Band of the CH3Radical

Pressure broadening coefficients for an infrared transition of the methyl radical have been measured for the first time. CH₃radicals, generated by pyrolyzing di-tert-butyl peroxide in a flow of either N₂or Ar, were probed using a tunable diode laser and a multipass absorption cell. The Lorentz half-width of theQ(6,6) line of the ν₂band of CH₃at 607.024 cm⁻¹was measured as a function of pressure at 295 K. The broadening coefficients (HWHM) areb(Ar) = 0.0310 ± 0.0012 cm⁻¹atm⁻¹andb(N₂) = 0.0390 ± 0.0020 cm⁻¹atm⁻¹. These coefficients are lower than those for CH₄–Ar, N₂broadening. This may be due to a lower polarizability or smaller effective hard collision diameter for CH₃relative to CH₄.     

TOTAL ASSIGNMENT OF 1H AND 13C NMR SPECTRA OF A BRIDGED TRIRUTHENIUM CLUSTER-POLYPYRIDINE DIMER BASED ON 2D (COSY,HMQC, AND HMBC) TECHNIQUES

The bridged ruthenium cluster-polypyridine dimer [Ru₃O(CH₃COO)₆(py)₂(tmbpy)Ru(bpy)₂(Cl)](PF₆)₂ (py = pyridine, = 2, 2′-bipyridine and tmbpy = 4, 4′-trimethylenedipyridine) has been synthesized and structurally characterized based on ¹H and ¹³C NMR spectroscopy. This species exhibits a complex pattern of NMR signals due to the presence of a paramagnetic [Ru₃O] core and seven non-equivalent aromatic rings. 2D NMR (COSY, HMQC and HMBC) correlation techniques have been required for the total assignment of the ¹H and ¹³C NMR spectra.     

The Vibrational Spectra of Complexes with Planar Monothiooxamides. IV. The Copper(II) and Copper(I) Complexes of Neutral Monothiooxamides

The new complexes CuX₂(LH₂), CuX₂ (SH₃) (X = Cl, Br), CuX(LH₂), CuX(SH₃) (X = Cl, Br, I), CuX(H₄MTO)₂ (X = Cl, Br), Cul(H₄MTO) and CuX(H₃MMTO)₂ (X = Cl, Br, I), where LH₂ = N.N′-dimethyl-monothiooxamide, SH₃ = N(s)-methylmonothiooxamide, H₄MTO = monothiooxamide and H₃MMTO = N_(o)-methylmonothiooxamide, have been prepared. The complexes were characterized by elemental analyses, conductivity measurements, magnetic moments and spectroscopic (UV/VIS, FT-IR, Laser-Raman) studies. The vibrational analysis of the complexes has been given using NH/ND, CH₃/CD₃ and ⁶³cu/⁶⁵cu isotopic substitutions. The neutral monothiooxamides behave as monodentate ligands in the Cu(I) complexes coordinating through their thioamide sulfur atom. The ligands LH2 and SH₃ act as bidentate chelating agents in the Cu(II) complexes with ligated atoms being the thioamide sulfur and the amide oxygen.     

EPR of Co+2 in Mg(CH3COO)2·4H2O

EPR spectra of the ⁵⁹Co⁺² ion in oriented crystals of Mg(CH₃COO)₂·4H₂O have been measured at 9.4 GHz and a temperature of 4.2 K. The data for each of the two metal ion sites per unit cell are well-described by a spin Hamiltonian for $\text{S =}\text{1}\text{2}\text{, I =}\text{7}\text{2}$ with g_x = 6.13, g_y = 389, g_z = 2.49 and A_x = 0.0193, A_y' = 0.075, A_z' = 0.0032 cm^?1. Only the x-axes of the g- and A-tensors coincide. Orientation of the principal directions relative to the crystal axes has been established for the g- and A-tensors at both sites. They are consistent with the weakly ferromagnetic canted antiferromagnetism found in Co(CH₃COO)₂·4H₂O below T_N ?85mK.     

Measurement of intensities of multiplets in the 2ν3-band of methane at low temperatures

The integrated intensities of the multiplets P(1)–P(10), R(0)–R(9), and of the Q-branch in the 2ν₃-band of ¹²CH₄ have been measured at 102°K, 152°K, 202°K, 251°K, and 300°K. Comparison of our data with theoretical line strengths confirms, at all of the temperatures mentioned, the intensity anomalies observed by Margolis⁽⁵⁾ for lines in this band. The integrated intensity of the 2ν₃-band is found to be S_v = (1·76±-0·04)(300/T (°K)) cm^?2 atm^?1.     

Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111)

The mechanism of ethanol decomposition on the Ni(111) surface has been investigated between 155 and 500 K. The sequence of bond scission steps which occur as ethanol undergoes dissociative reactions on this surface has been deduced using deuterium and ¹³C isotopic labels. Bond activation occurs in the order (1) OH, (2) CH₂ (methylene CH), (3) CC, (4) CH₃ (methyl CH). The products observed are CH₃CHO(g), CH₄(g), CO(g), H₂(g) and surface carbon, C(a). The latter species exhibits a carbidic AES lineshape in the temperature range 450 to 670 K, at which temperature it dissolves into the Ni bulk. Acetaldehyde, CH₃CHO, and methane, CH₄, desorb with the same threshold temperature (260–265 K), and the formation of both of these products is controlled by scission of the methylene CH bond (CH₂ group). The CH₃ group is cleaved from the intermediate surface CH₃CHO species to form CH₃(ads). H₂ exhibits a broad, doublet desorption peak from 300 to 450 K. The carbonoxygen bond in ethanol remains intact and CO ultimately desorbs in a single desorption limited process (T_p = 430 K). A small fraction of CO(a) species undergo exchange with the carbidic surface carbon in a minor process observed above 440 K.