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The reaction of nickel(II) chloride with 3-meth-oxy-aniline yielded di-chlorido-tetra-kis-(3-meth-oxy-aniline)nickel(II), [NiCl2(C7H9NO)4], as yellow crystals. The NiII ion is pseudo-octa-hedral with the chloride ions trans to each other. The four 3-meth-oxy-aniline ligands differ primarily due to different conformations about the Ni-N bond, which also affect the hydrogen bonding. Inter-molecular N-H⋯ Cl hydrogen bonds and short Cl⋯Cl contacts between mol-ecules link them into chains parallel to the b axis.

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Introduction: Expression of light sensitive ion channels by selected neurons has been achieved by viral mediated transduction with gene constructs, but for this to have therapeutic uses, for instance in treating epilepsy, any adverse effects of viral infection on the cerebral cortex needs to be evaluated. Here, we assessed the impact of adeno-associated virus 8 (AAV8) carrying DNA code for a soma targeting light activated chloride channel/FusionRed (FR) construct under the CKIIa promoter. Methods: Viral constructs were harvested from transfected HEK293 cells in vitro and purified. To test functionality of the opsin, cultured rodent neurons were transduced and the light response of transduced neurons was assayed using whole-cell patch-clamp recordings. In vivo expression was confirmed by immunofluorescence for FR. Unilateral intracranial injections of the viral construct were made into the mouse neocortex and non-invasive fluorescence imaging of FR expression made over 1-4 weeks post-injection using an IVIS Spectrum system. Sections were also prepared from injected mouse cortex for immunofluorescence staining of FR, alongside glial and neuronal marker proteins. Results: In vitro, cortical neurons were successfully transduced, showing appropriate physiological responses to light stimulation. Following injections in vivo, transduction was progressively established around a focal injection site over a 4-week period with spread of transduction proportional to the concentration of virus introduced. Elevated GFAP immunoreactivity, a marker for reactive astrocytes, was detected near injection sites associated with, and proportional to, local FR expression. Similarly, we observed reactive microglia around FR expressing cells. However, we found that the numbers of NeuN+ neurons were conserved close to the injection site, indicating that there was little or no neuronal loss. In control mice, injected with saline only, astrocytosis and microgliosis was limited to the immediate vicinity of the injection site. Injections of opsin negative viral constructs resulted in comparable levels of astrocytic reaction as seen with opsin positive constructs. Discussion: We conclude that introduction of an AAV8 vector transducing expression of a transgene under a neuron specific promotor evokes a mild inflammatory reaction in cortical tissue without causing extensive short-term neuronal loss. The expression of an opsin in addition to a fluorescent protein does not significantly increase neuroinflammation.

RESUMEN

The reaction of CuCl2 with 1,6-diphenyl-1,3,5,6-hexa-netetrone and 2,2'-bi-pyridine (bipy) in ethanol gave crystals of the corresponding bimetallic complex, [Cu2(C18H12O4)Cl2(C10H8N2)2]·2H2O. The mol-ecule is centrosymmetric with each CuII ion coordinated to two oxygen atoms from the tetronediate, two nitro-gen atoms from a bipy ligand and one coordinated chloride ion. A water mol-ecule of crystallization forms hydrogen bonds to the chloride ions, linking the mol-ecules into a chain parallel to the bc-face diagonal.

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Crystals of the new organic-inorganic material (DAP-H2)[CuBr4] (1); (DAP = hexahydrodiazepine (C5H14N2)) were successfully synthesized by slow evaporation and characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermal analysis, UV-Vis-NIR diffuse reflectance spectroscopy, and magnetic measurements. X-ray investigation demonstrates that 1 crystallizes in the monoclinic space group C2/c. The supramolecular crystal structure of 1 is guided by several types of hydrogen bonding which connect anions and cations together into a three-dimensional network. The optical band gap was determined by diffuse reflectance spectroscopy to be 1.78 eV for a direct allowed transition, implying that it is suitable for light harvesting in solar cells. The vibrational properties of this compound were studied by infrared spectroscopy, while its thermal stability was established by simultaneous TGA-DTA from ambient temperature to 600 °C. The study of the photoresponse behavior of an optoelectronic device, based on (C5H14N2)[CuBr4], has shown a power conversion efficiency (PCE) of 0.0017%, with J sc = 0.0208 mA/cm2, V oc = 313.7 mV, and FF = 25.46. Temperature dependent magnetic susceptibility measurements in the temperature range 1.8-310 K reveal weak antiferromagnetic interactions via the two-halide superexchange pathway [2J/k B = -8.4(3) K].

RESUMEN

Halide-bridged polymers have gained significant interest due to their diverse properties and potential applications. Stacked Cu2L2X4 dimers, where L is an organic ligand and X can be Cl- or Br-, are of interest because a chloride analogue where L = 2-pyridone, had previously been reported to exhibit bulk ferromagnetism, which augured great potentiality for this class of compounds. The synthesis, structural characterization, magnetic susceptibility measurements, and computational studies of two isostructural CuClMI (MI = methylisothiazolinone) and CuBrMI polymers of Cu(II), along with a related CuClPYR (PYR = 2-pyridone) is reported. CuClMI and CuBrMI were found to exhibit AFM bulk properties, due to FM/AFM alternating chains along the halide-bridged polymer axis, while FM bulk properties were confirmed for CuClPYR exhibiting a FM spin ladder. In combination with a benzamide analogue, CuClBA, three O-donor amides, CuClMI, CuClBA and CuClPYR were analyzed and revealed that the kinetic exchange is affected by the identity, but more importantly, the orientation of the satellite ligands. The torsional angle of the ligand with the dimer plane is shown to significantly affect the magnetic exchange in the dimer, and between dimers, explaining the reported FM bulk properties of CuClPYR. This finding is exceedingly important, as it suggests that a spin device can be constructed to flip between singlet/triplet states by manipulating the orientation of the satellite/terminal ligand.

RESUMEN

Quantum phase transitions in quantum matter occur at zero temperature between distinct ground states by tuning a nonthermal control parameter. Often, they can be accurately described within the Landau theory of phase transitions, similarly to conventional thermal phase transitions. However, this picture can break down under certain circumstances. Here, we present a comprehensive study of the effect of hydrostatic pressure on the magnetic structure and spin dynamics of the spin-1/2 ladder compound C9H18N2CuBr4. Single-crystal heat capacity and neutron diffraction measurements reveal that the Néel-ordered phase breaks down beyond a critical pressure of Pc ∼ 1.0 GPa through a continuous quantum phase transition. Estimates of the critical exponents suggest that this transition may fall outside the traditional Landau paradigm. The inelastic neutron scattering spectra at 1.3 GPa are characterized by two well-separated gapped modes, including one continuum-like and another resolution-limited excitation in distinct scattering channels, which further indicates an exotic quantum-disordered phase above Pc.

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Syntheses are described for the blue/purple complexes of cobalt(II) chloride with the tetra-dentate ligands 1,4-bis-[2-(pyridin-2-yl)eth-yl]piperazine (Ppz), 1,4-bis-[2-(pyridin-2-yl)eth-yl]homopiperazine (Phpz), trans-2,5-dimethyl-1,4-bis-[2-(pyridin-2-yl)eth-yl]piperazine (Pdmpz) and tridentate 4-methyl-1-[2-(pyridin-2-yl)eth-yl]homopiperazine (Pmhpz). The CoCl2 complexes with Ppz, namely, {µ-1,4-bis-[2-(pyridin-2-yl)eth-yl]piperazine}bis-[di-chlorido-cobalt(II)], [Co2Cl4(C18H24N4)] or Co2(Ppz)Cl4, and Pdmpz (structure not reported as X-ray quality crystals were not obtained), are shown to be dinuclear, with the ligands bridging the two tetra-hedrally coordinated CoCl2 units. Co2(Ppz)Cl4 and {di-chlorido-{4-methyl-1-[2-(pyridin-2-yl)eth-yl]-1,4-di-aza-cyclo-hepta-ne}cobalt(II) [CoCl2(C13H21N3)] or Co(Pmhpz)Cl2, crystallize in the monoclinic space group P21/n, while crystals of the penta-coordinate mono-chloro chelate 1,4-bis-[2-(pyr-id-in-2-yl)eth-yl]piperazine}chlorido-cobalt(II) perchlorate, [CoCl(C18H24N4)]ClO4 or [Co(Ppz)Cl]ClO4, are also monoclinic (P21). The complex {1,4-bis-[2-(pyridin-2-yl)eth-yl]-1,4-di-aza-cyclo-hepta-ne}di-chlorido-cobalt(II) [CoCl2(C19H26N4)] or Co(Phpz)Cl2 (P ) is mononuclear, with a penta-coordinated CoII ion, and entails a Phpz ligand acting in a tridentate fashion, with one of the pyridyl moieties dangling and non-coordinated; its displacement by Cl- is attributed to the solvophobicity of Cl- toward MeOH. The penta-coordinate Co atoms in Co(Phpz)Cl2, [Co(Ppz)Cl]+ and Co(Pmhpz)Cl2 have substantial trigonal-bipyramidal character in their stereochemistry. Visible- and near-infrared-region electronic spectra are used to differentiate the two types of coordination spheres. TDDFT calculations suggest that the visible/NIR region transitions contain contributions from MLCT and LMCT character, as well as their expected d-d nature. For Co(Pmhpz)Cl2 and Co(Phpz)Cl2, variable-temperature magnetic susceptibility data were obtained, and the observed decreases in moment with decreasing temperature were modelled with a zero-field-splitting approach, the D values being +28 and +39 cm-1, respectively, with the S = 1/2 state at lower energy.

RESUMEN

The crystal structure and magnetic properties of two all-pyrazine-bridged antiferromagnetic spin ladders are reported. The complexes, catena-(bis(3-X-4-pyridone)(µ-pyrazine)copper(II)(-µ-pyrazine)diperchlorate ([Cu(pz)1.5(L)2](ClO4)2 where L = 3-X-4-pyridone and X = Br (1) or Cl (2)), contain copper(II)-based ladders in which both the rung and rail bridges are pyrazine molecules bonded through the x2-y2 orbital of the copper(II) ions. This structural scaffold is proposed to approach the isotropic spin-ladder regime. 1 and 2 crystallize in the monoclinic space group P21/c. Due to the bulk of the 3-X-4-HOpy ligands, the ladders are well isolated in the a-direction (1, 15.6 Å; 2, 15.5 Å). The ladders, which run in the b-direction, are stacked in the c-direction with the separation (1, 7.87 Å; 2, 7.82 Å) between copper(II) ions caused by the bulk of a semi-coordinate perchlorate ion coordinated in the axial position. Computational evaluation of magnetic JAB couplings between Cu-moieties of 2 supports the experimentally proposed magnetic topology and agrees with an isolated isotropic spin-ladder (Jrail = -4.04 cm-1 (-5.77 K) and Jrung = -3.89 cm-1 (-5.56 K)). These complexes introduce a convenient scaffold for synthesizing isotropic spin-ladders with modest superexchange interactions, the strength of which may be tuned by variations in L. The magnetic susceptibility down to 1.8 K, for both compounds, is well described by the strong-rung ladder model giving nearly isotropic exchange with Jrung ≈ Jrail ≈ -5.5 K (1) and -5.9 K (2) using the Hamiltonian. Theoretical simulations of the magnetic response of 2 using the isotropic ladder model are in excellent agreement with experiment. The measured magnetization to 5 T indicates a quantum-dominated magnetic spectrum. Again, calculated lower and saturation (4.3 and 24 T, respectively) critical fields for 2 are consistent with experimental measurements, and magnetization data at very low temperatures indeed suggest the presence of quantum effects. Further, the computational study of short- and long-range spin ordering indicates that a 2D-to-3D crossover might be feasible at lower temperatures. Analysis of the Boltzmann population corroborates the presence of accessible triplet states above the singlet ground state enabling the aforementioned 2D-to-3D crossover.

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Neuromodulation is an established treatment for numerous neurological conditions, but to expand the therapeutic scope there is a need to improve the spatial, temporal and cell-type specificity of stimulation. Optogenetics is a promising area of current research, enabling optical stimulation of genetically-defined cell types without interfering with concurrent electrical recording for closed-loop control of neural activity. We are developing an open-source system to provide a platform for closed-loop optogenetic neuromodulation, incorporating custom integrated circuitry for recording and stimulation, real-time closed-loop algorithms running on a microcontroller and experimental control via a PC interface. We include commercial components to validate performance, with the ultimate aim of translating this approach to humans. In the meantime our system is flexible and expandable for use in a variety of preclinical neuroscientific applications. The platform consists of a Controlling Abnormal Network Dynamics using Optogenetics (CANDO) Control System (CS) that interfaces with up to four CANDO headstages responsible for electrical recording and optical stimulation through custom CANDO LED optrodes. Control of the hardware, inbuilt algorithms and data acquisition is enabled via the CANDO GUI (Graphical User Interface). Here we describe the design and implementation of this system, and demonstrate how it can be used to modulate neuronal oscillations in vitro and in vivo.

RESUMEN

The two complexes Cu(2ip)X2 were prepared (where 2ip = 2-iodopyridine and X = Cl or Br), and their crystal structures were determined. The two complexes are isomorphous and form a magnetic chain based on the two-halide exchange pathway. The powder and single crystal magnetic susceptibility data were measured down to 1.8 K. The exchange is antiferromagnetic along the chain; the exchange is stronger in the bromide complex than in the corresponding chloride complex. In the ordered state, weak moments appear along some of the axes, indicative of spin-canting. The calculated spin densities and the mapped surface of spin density on total electron density were used to rationalize qualitatively the observed magnetic behavior. Low temperature structures are compared with the room temperature data; the C-IX-Cu and Cu-XX-Cu distances are shorter at low temperatures; in contrast, the covalent bonds of the organic ligand (2-iodopyridine) are longer (negative thermal expansion of the covalent bonds). The anomalous behavior is rationalized using charge transfer from Cu-X group to the anti-bonding orbital of the organic ligand. Quantum theory of atoms in molecules was used to analyze C-IX halogen bonding interactions.

RESUMEN

A family of pyrazine-bridged, linear chain complexes of Cu(ii) of the formula [CuL2(H2O)2(pz)](ClO4)2 [pz = pyrazine; L = n-methyl-2(1H)-pyridone, n = 3 (1), 5 (2), and 6 (3)] has been prepared. Single-crystal X-ray diffraction shows six-coordinate, pyrazine-bridged chains with trans-pairs of ancillary ligands. The substituted pyridine molecules exist in their pyridone tautomers and are coordinated through the carbonyl oxygen atom. The structure is stabilized by intramolecular hydrogen bonds between the pyridone and water molecule, and via hydrogen bonds between the water molecules and perchlorate ions. 2 undergoes a crystallographic phase transition between C2/c (high temperature phase) and P1[combining macron] (low temperature phase). Powder EPR spectra reveal that all complexes are rhombic, although differences between gx and gy can only be seen clearly at Q-band. Variable temperature magnetic susceptibility data show antiferromagnetic interactions and the data were fit to the uniform chain model yielding J/kB = -9.8, -9.2 and -11 K for 1-3 respectively. Attempts to model an interchain interaction strength indicate that the chains are very well isolated.

RESUMEN

The title compound H2L(CuCl3H2O)Cl (H2L = 1-(4'-pyridinium)pyridin-4-ol-ium), 1) was synthesized and investigated structurally and magnetically as well as via a first-principles, bottom-up theoretical analysis of the potential magnetic superexchange pathways. Compound 1 can be described structurally as a well-isolated, distorted 2D-honeycomb lattice with two potential exchange pathways: a dimeric interaction via hydrogen-bonded pairs of (CuCl3H2O) ions and a chain structure via bridging chloride ions. Surprisingly, the experimental magnetic data are best fitted using both a simple dimer model with a Curie-Weiss correction for interdimer exchange (Jdimer = -107.4(1) K, θ = -1.22(4) K) and a strong-rung ladder model (Jrung = -105.8(7) K, Jrail = 2(7) K). Theoretical analysis at the UB3LYP/6-31+G(d) level supports the strong exchange observed through the [CuCl4(H2O)]2- dimer moiety superexchange pathway (-102 K = -71 cm-1). However, the apparent vanishingly small exchange through the single halide bridge is merely a brute average of competing ferromagnetic (FM) (+24.8 K = +17.0 cm-1) and antiferromagnetic (AFM) (-21.0 K = -14.6 cm-1) exchange interactions. Our computational study shows that these fitting parameters carry no physical meaning since a honeycomb plaquette must be taken as magnetic building block for 1. The competition between FM and AFM pair interactions leads to geometrical frustration in 1 and could induce interesting magnetic response at low temperatures, if the magnetic exchange is adequately tuned by modifying substituents in ligands and, in turn, interactions within the crystal packing.

RESUMEN

Brain-machine Interfaces (BMI) hold great potential for treating neurological disorders such as epilepsy. Technological progress is allowing for a shift from open-loop, pacemaker-class, intervention towards fully closed-loop neural control systems. Low power programmable processing systems are therefore required which can operate within the thermal window of 2° C for medical implants and maintain long battery life. In this work, we have developed a low power neural engine with an optimized set of algorithms which can operate under a power cycling domain. We have integrated our system with a custom-designed brain implant chip and demonstrated the operational applicability to the closed-loop modulating neural activities in in-vitro and in-vivo brain tissues: the local field potentials can be modulated at required central frequency ranges. Also, both a freely-moving non-human primate (24-hour) and a rodent (1-hour) in-vivo experiments were performed to show system reliable recording performance. The overall system consumes only 2.93 mA during operation with a biological recording frequency 50 Hz sampling rate (the lifespan is approximately 56 hours). A library of algorithms has been implemented in terms of detection, suppression and optical intervention to allow for exploratory applications in different neurological disorders. Thermal experiments demonstrated that operation creates minimal heating as well as battery performance exceeding 24 hours on a freely moving rodent. Therefore, this technology shows great capabilities for both neuroscience in-vitro/in-vivo applications and medical implantable processing units.

Asunto(s)

RESUMEN

Low-dimensional quantum magnets promote strong correlations between magnetic moments that lead to fascinating quantum phenomena. A particularly interesting system is the antiferromagnetic spin-1/2 Heisenberg chain because it is exactly solvable by the Bethe-Ansatz method. It is approximately realized in the magnetic insulator copper pyrazine dinitrate, providing a unique opportunity for a quantitative comparison between theory and experiment. We investigate its thermodynamic properties with a particular focus on the field-induced quantum phase transition. Thermal expansion, magnetostriction, specific heat, magnetization, and magnetocaloric measurements are found to be in excellent agreement with exact Bethe-Ansatz predictions. Close to the critical field, thermodynamics obeys the expected quantum critical scaling behavior, and in particular, the magnetocaloric effect and the Grüneisen parameters diverge in a characteristic manner. Beyond its importance for quantum magnetism, our study establishes a paradigm of a quantum phase transition, which illustrates fundamental principles of quantum critical thermodynamics.

RESUMEN

The synthesis, structure, magnetic properties, and theoretical analysis of a new phase of dichloro(2-chloro-3-methylpyridine)copper(II) (2) and its isomorphous analogue dichloro(2-bromo-3-methylpyridine)copper(II) (3) are reported. Both complexes crystallize in the orthorhombic space group Pbca and present square pyramidal Cu(II) ions bridged into chains by chloride ions with each copper(II) bearing a single pyridine ligand. Variable temperature magnetic susceptibility measurements were well fit by a uniform one-dimensional ferromagnetic chain model with 2, J = 69.0(7) K, C = 0.487 emu-K/mol-Oe; 3, J = 73.9(4) K, C = 0.463 emu-K/mol-Oe (H = -JΣSi·Sj Hamiltonian). The experimental J-values were confirmed via theoretical calculations. Comparison to a known disordered polymorph of dichloro(2-chloro-3-methylpyridine)copper(II), 1, shows marked differences as there are significant antiferromagnetic next-nearest neighbor interactions in 1 in addition to randomness induced by the disorder which provide a distinctly different magnetic response. The differences in magnetic behavior are attributed principally to the structural difference in the Cu(II) coordination sphere, 1 being significantly closer to trigonal-bipyramidal, whose difference changes both the nearest and next-nearest neighbor interactions.

RESUMEN

Dithiazolyl (DTA)-based radicals have furnished many examples of organic spin-transition materials, some of them occurring with hysteresis and some others without. Herein, we present a combined computational and experimental study aimed at deciphering the factors controlling the existence or absence of hysteresis by comparing the phase transitions of 4-cyanobenzo-1,3,2-dithiazolyl and 1,3,5-trithia-2,4,6-triazapentalenyl radicals, which are prototypical examples of non-bistable and bistable spin transitions, respectively. Both materials present low-temperature diamagnetic and high-temperature paramagnetic structures, characterized by dimerized (⋅⋅⋅A-A⋅⋅⋅A-A⋅⋅⋅)n and regular (⋅⋅⋅A⋅⋅⋅A⋅⋅⋅A⋅⋅⋅A⋅⋅⋅)n π-stacks of radicals, respectively. We show that the regular π-stacks are not potential energy minima but average structures arising from a dynamic inter-conversion between two degenerate dimerized configurations: (⋅⋅⋅A-A⋅⋅⋅A-A⋅⋅⋅)n ↔(-A⋅⋅⋅A-A⋅⋅⋅A-)n . The emergence of this intra-stack dynamics upon heating gives rise to a second-order phase transition that is responsible for the change in the dominant magnetic interactions of the system. This suggests that the promotion of a (⋅⋅⋅A-A⋅⋅⋅A-A⋅⋅⋅)n ↔(-A⋅⋅⋅A-A⋅⋅⋅A-)n dynamics is a general mechanism for triggering spin transitions in DTA-based materials. Yet, this intra-stack dynamics does not suffice to generate bistability, which also requires a rearrangement of the intermolecular bonds between the π-stacks via a first-order phase transition.

RESUMEN

The reactions of copper(ii) carboxylate sources with acetylacetone dioxime (acacdoH2) in Me2CO have been studied and a novel, metal ion-assisted ligand transformation has been discovered. The reaction of [Cu2(diba)4(dibaH)2] and acacdoH2 (1 : 1.5) in Me2CO has provided access to the complex {[Cu2(diba)4(qunx)]}n (1) in low yield (25-30%), where dibaH is 3,3-dimethylbutyric acid and qunx is quinoxaline. The [Cu2(piv)4(pivH)2]/acacdoH2 (1 : 1.5) reaction system in warm Me2CO, where pivH is pivalic acid, gave the analogous complex {[Cu2(piv)4(qunx)]}n (2) in moderate yield (∼50%). Complexes 1 and 2 can be easily prepared by the direct 1 : 1 reactions between the corresponding copper(ii) carboxylate starting materials and qunx in Me2CO and MeOH, respectively. The formation of coordinated qunx in 1 and 2 is CuII-promoted (assisted) as suggested by the failure to synthesize the free qunx by a variety of reactions of acacdoH2 and Me2CO under aerobic conditions in the absence or even the presence of dibaH and pivH, respectively. The observed acacdoH2 → qunx transformation is catalytic and new in the chemistry of the dioximes of ß-diketones, and a mechanism has been proposed based on well-established reactions of organic chemistry. The mechanism is based on a double Beckmann rearrangement-type transformation and the overall scheme is represented by the 1 : 1 : 1 reaction between acacdoH2, Me2CO and O2. Complexes 1 and 2 have similar molecular structures consisting of paddle-wheel {Cu2(η1:η1:µ-O2CR)4} units bridged by qunx ligands in a zigzag 1D chain arrangement. The geometry of the CuII ions is square pyramidal with a quinoxaline nitrogen atom occupying the apical position at each metal ion. Weak H bonds are present within the chains, the donors being qunx carbon atoms and the acceptors being coordinated carboxylate oxygen atoms. Neighbouring chains interact through C-Hπ interactions between diba-/piv- methyl groups and the "pyrazine" part of qunx forming layers which are stacked along the b (1) or a (2) axis through weak van der Waals interactions. The packing of the layers is different in the two structures, due to the different nature of the carboxylate ligands. Hirshfeld surface analysis of the two structures reveals the similarity of the interchain (intralayer) interactions. The IR and Raman data of 1 and 2 are discussed in terms of the coordination mode of the carboxylate groups and permit assignments of some characteristic bands/peaks of coordinated qunx. Dc magnetic susceptibility studies in the 1.8-310 K range reveal very strong antiferromagnetic CuIICuII exchange interactions within the carboxylate-bridged Cu2 units (J = -479 K for 1 and -532 K for 2 using the H = - J∑S1·S2 spin Hamiltonian) and weaker antiferromagnetic interactions between the Cu2 units via the qunx superexchange pathways, with the latter being ∼10% in strength compared to the former. A critical discussion of the acacdoH2 → qunx transformation in 1 and 2 is provided in the light of other impressive, recently discovered CuII-assisted transformations of acacdoH2, pointing out the key role of the solvent in the processes known to date.

RESUMEN

The synthesis, crystal structure, and magnetic properties (from a combined experimental and First-Principles Bottom-Up theoretical study) of the new compound catena-dichloro(2-Cl-3Mpy)copper(II), 1, [2-Cl-3Mpy=2-chloro-3-methylpyridine] are described and rationalized. Crystals of 1 present well isolated magnetic 1D chains (no 3D order was experimentally observed down to 1.8 K) and magnetic frustration stemming from competing ferromagnetic nearest-neighbor (J(NN)) interactions and antiferromagnetic next-nearest neighbor (J(NNN)) interactions, in which α=J(NNN)/J(NN) <-0.25. These magnetic interactions give rise to a unique magnetic topology: a two-leg zigzag ladder composed of edge-sharing up-down triangles with antiferromagnetic interactions along the rails and ferromagnetic interactions along the zigzag chain that connects the rails. Crystals of 1 also present a random distribution of the 2-Cl-3Mpy groups, which are arranged in two different orientations, each with a 50 % occupancy. This translates into a random static structural disorder within each chain by virtue of which the value of the J(NN) magnetic interactions can randomly take one of the following three values: 53, 36, and 16 cm(-1). The structural disorder does not affect the J(NNN) value, which in all cases is approximately -9 cm(-1). A proper statistical treatment of this disorder provides a computed magnetic susceptibility curve that reproduces the main features of the experimental data.

RESUMEN

Reaction of 4-methoxyacetophenone with diethyl oxalate under basic conditions produced 3,4-dihydroxy-1,6-bis(4-methoxyphenyl)hexa-2,4-diene-1,6-dione, C20H18O6, (1). The molecules lie across a crystallographic inversion centre and intramolecular hydrogen bonding, similar to acetylacetone, is observed, confirming that the molecule is in the di-enol-dione tautomeric form. Additional O-H...O hydrogen bonds link the molecules into chains parallel to the b axis. The structure is compared with that of redetermined 4-methylphenyl compound 3,4-dihydroxy-1,6-bis(4-methylphenyl)hexa-2,4-diene-1,6-dione, C20H18O4, (2), which crystallizes in a similar fashion. The salt, catena-poly[[µ2-2-hydroxy-4-(4-methoxyphenyl)-4-oxobut-2-enoato-κ(3)O(1),O(2):O(4)][µ2-2-hydroxy-4-(4-methoxyphenyl)-4-oxobut-2-enoic acid-κ(2)O(1):O(4)]potassium], [K(C11H9O5)(C11H10O5)]n, (3), was isolated as a by-product of the synthesis of (1). The two organic species are linked by a strong hydrogen bond between the carboxylic acid and carboxylate groups. They are further stabilized and linked into a double-chain structure via the seven-coordinate potassium ion.

RESUMEN

A complete first-principles bottom-up computational study of the magnetic properties of [Cu(pz)2](ClO4)2 is presented. A remarkable agreement is observed in the whole range of temperatures between simulated and experimental magnetic susceptibility data. Interestingly, the simulated heat capacity values show an anomaly close to the Néel temperature of 4.21 K associated with a transition from a two-dimensional (2D) antiferromagnet to a three-dimensional (3D) ordered state. The antiferromagnetic behavior of [Cu(pz)2](ClO4)2 is due to a 2D magnetic topology owing to two antiferromagnetic J(AB) interactions through pyrazine ligands. Although presenting a very similar molecular arrangement, the numerical values of the two magnetically significant J(AB) couplings differ by 25% (-10.2 vs -7.3 cm(-1)). This difference can be ascribed to three main contributions: (i) the central pyrazine ring shearing-like distortion, (ii) the effect of the orientation of the perchlorate counterions, and (iii) a hitherto unrecognized skeleton-counterion cooperation arising from different hydrogen bonding contributions in the two most significant J(AB) couplings. The impact of the orientation of the perchlorate counterions is disclosed by comparison to J(AB) studies using structurally similar ligands but with different electronegativity (namely, BF4(-), BCl4(-), and BBr4(-)). Pyrazine ligands and perchlorate counterions prove to be noninnocent.