Effect of the linking bridge type on the self-assembly behaviour of 2',3'-difluoroterphenyl derivatives.

The self-assembly behaviour and the crystallization kinetics of two liquid crystal compounds containing 2',3'-difluorosubstituted terphenyl as the mesogenic core have been described. Calorimetric studies show that the linking bridge type affects the polymorphism of smectic phases. The CH2O.3 compound with the -CH2O- linking bridge connected with a longer methylene spacer possesses the chiral smectic phase with antiferroelectric properties (SmCA* phase), while the COO.6 liquid crystal with the -COO- linking bridge connected with a shorter alkyl chain forms the chiral smectic phase with ferroelectric properties (SmC* phase). Both compounds crystallize upon slow cooling, while fast cooling causes the vitrification of the conformationally disordered crystal phase. Dielectric measurements reveal the complex relaxation dynamics in the identified thermodynamic states. DFT calculations allow us to estimate the nature of relaxation processes.

A Siamese neural network framework for glass transition recognition.

A Siamese neural network, which is a deep learning technique, was applied to investigate phase transitions based on polarising microscopic textures of liquid crystals like: antiferroelectric smectic CA* phase and its glass, smectic I phase and its glass, and smectic G and its glass. It is an example of a subtle transition without significant structural changes, where textures above and below the glass transition temperature are similar. The Siamese neural network could distinguish textures of the chosen liquid crystal phases from a glass of that phase. This publication provides details of the Siamese neural network and its implementation based on three different convolutional neural networks has been tested.

Influence of proton irradiation on the magnetic properties of two-dimensional Ni(II) molecular magnet.

The influence of 1.9 MeV proton irradiation on structural and magnetic properties has been explored in the two-dimensional (2D) NiSO4(1,3-phenylenediamine)2 coordination ferrimagnet. The X-ray powder diffraction and IR spectroscopy revealed that the octahedrons with Ni ion in the center remain unchanged regardless of the fluence a sample received. In contrast, proton irradiation greatly influences the hydrogen bonds in the flexible parts in which the 1,3-phenylenediamine is involved. Dc magnetic measurements revealed that several magnetic properties were modified with proton irradiation. The isothermal magnetization measured at T = 2.0 K varied with the proton dose, achieving a 50% increase in magnetization in the highest measured field µ0Hdc = 7 T or a 25% decrease in remanence. The most significant change was observed for the coercive field, which was reduced by 90% compared to the non-irradiated sample. The observed results are accounted for the increased freedom of magnetic moments rotation and the modification of intralayer exchange couplings.

Vitrification of the smectic CA* phase and kinetics of cold crystallization investigated for a fluorinated compound with a chiral centre based on (S)-(+)-3-octanol.

The formation of glass of the anticlinic high-tilted smectic CA* phase even at low cooling rates (≥2 K min-1) is reported for (S)-4'-(1-ethylhexyloxycarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy)pentyl-1-oxy]benzoate. The kinetics of crystallization is investigated via differential scanning calorimetry, polarizing optical microscopy and broadband dielectric spectroscopy. The temperature region of the largest crystallization rate, the activation energy of cold crystallization and the energy barrier of nucleation are determined. The coupling of the characteristic crystallization time with the α-relaxation time is studied. A high fragility index equal to 139 is obtained for this glassformer. Comparison with a very similar glassforming compound, with the chiral centre based on (S)-(+)-2-octanol instead of (S)-(+)-3-octanol, is presented.

Investigation of Chiral Smectic Phases and Conformationally Disordered Crystal Phases of the Liquid Crystalline 3F5FPhH6 Compound Partially Fluorinated at the Terminal Chain and Rigid Core.

Complementary methods are applied to investigate the phase transitions and crystallization kinetics of the liquid crystalline compound denoted as 3F5FPhH6. Two crystal phases are confirmed, and one of them is the conformationally disordered (CONDIS) phase. Complexity of the melt crystallization process is revealed by the analysis with Friedman's isoconversional method. The melt crystallization of 3F5FPhH6 shows different mechanisms depending on temperature, which is explained by the relation between the thermodynamic driving force and the thermal energy of translational degrees of freedom. The studied compound crystallizes even during fast cooling (30 K/min), unlike similar compounds with different fluorosubstitutions of the benzene ring, which form the smectic glass for moderate cooling rates. The tendency to vitrification of the smectic phase decreases apparently with the decreasing stability width of the SmCA* phase and the increasing relaxation time of the collective relaxation process in this phase, at least for homologues differing from 3F5FPhH6 only by the type of fluorosubstitution.

Vibrational dynamics of ethosuximide polymorphs. Infrared absorption and inelastic neutron scattering spectroscopy and model calculations.

Commercially available and administered to the patients ethosuximide is a racemic mixture of two enantiomers, each of them exist in different conformations. The presence of the species mentioned are proven by the title experimental methods aided by DFT model calculations. Results of the latter are matched against spectroscopic data by the clustering window analysis. One type of hydrogen bonds exist in the solid forms of ethosuximide NH⋯O, leading to the polymorphic variety of the substance studied.

Comparative study of electrooptic, dielectric, and structural properties of two glassforming antiferroelectric mixtures with a high tilt angle.

Vitrification of the antiferroelectric smectic-C_{A}^{*} phase is reported for the orthoconic mixture W-1000 and its new derivative W-356. The crystallization is not observed even upon slow cooling and the cold crystallization on subsequent heating is also absent. Molecular dynamics in the smectic phases of both mixtures is investigated down to 173 K and the fragility parameters are determined from the temperature behavior of the α-process. X-ray diffraction is applied to compare the structural parameters of W-356 and W-1000 as well as to study the structural changes during the glass transition of the Sm-C_{A}^{*} phase. The evolution of the smectic layer order within the Sm-C_{A}^{*} glass is reported, while the correlation length of the short-range order in the smectic layers is shown to be almost constant below the glass transition temperature. Electrooptic properties of W-356: spontaneous polarization, tilt angle and switching time are determined and compared with these of W-1000. The observed differences between the properties of W-356 and W-1000 might be explained by the dimer formation of components with the -C≡N terminal group, present only in the W-356 mixture, and by the different structure of the aromatic molecular core in one of the W-356 components.

On relaxation and vibrational dynamics in the thermodynamic states of a chiral smectogenic glass-former.

This article shows the full characteristics (i.e., the phase situation as well as the relaxation and vibrational dynamics) of the (S)-4'-(1-methyloctyloxycarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy)pentyl-1-oxy]-benzoate chiral liquid crystal. Besides two enantiotropic chiral smectic phases (SmC* and ), the compound under study also forms the hexatic smectic phase and two crystal phases (Cr1 and Cr2). The XRD patterns imply a similar structure of both crystal phases. The sample crystallizes upon slow cooling, while the phase undergoes a glass transition during fast cooling. Upon subsequent heating, cold crystallization is observed. Our research reveals the complex relaxation dynamics in the identified thermodynamic states, e.g., two relaxations up to the beginning of cold crystallization, three modes in the crystal phases and seven processes in all smectic phases. The results from the scaling of the dielectric response indicate that the origin of the dynamics and behavior of the dielectric permittivity is the same for all phases, regardless of the change in temperature and/or external biasing field. The high value of the fragility index (mf ≈ 146) indicates that the compound under study is a fragile glass-forming system. The region of the -COO- and -COC- group stretching vibrations is primarily sensitive to the structural changes occurring during phase transitions.

Description of Release Process of Doxorubicin from Modified Carbon Nanotubes.

The article discusses the release process of doxorubicin hydrochloride (DOX) from multi-wall carbon nanotubes (MWCNTs). The studies described a probable mechanism of release and actions between the surface of functionalized MWCNTs and anticancer drugs. The surface of carbon nanotubes (CNTs) has been modified via treatment in nitric acid to optimize the adsorption and release process. The modification efficiency and physicochemical properties of the MWCNTs+DOX system were analyzed by using SEM, TEM, EDS, FTIR, Raman Spectroscopy and UV-Vis methods. Based on computer simulations at pH 7.4 and the experiment at pH 5.4, the kinetics and the mechanism of DOX release from MWNT were discussed. It has been experimentally observed that the acidic pH (5.4) is appropriate for the efficient release of the drug from CNTs. It was noted that under acidic pH conditions, which is typical for the tumour microenvironment almost 90% of the drug was released in a relatively short time. The kinetics models based on different mathematical functions were used to describe the release mechanism of drugs from MWCNTs. Our studies indicated that the best fit of experimental kinetic curves of release has been observed for the Power-law model and the fitted parameters suggest that the drug release mechanism of DOX from MWCNTs is controlled by Fickian diffusion. Molecular dynamics simulations, on the other hand, have shown that in a neutral pH solution, which is close to the blood pH, the release process does not occur keeping the aggregation level constant. The presented studies have shown that MWCNTs are promising carriers of anticancer drugs that, depending on the surface modification, can exhibit different adsorption mechanisms and release.

Investigation of crystallization kinetics and its relationship with molecular dynamics for chiral fluorinated glassforming smectogen 3F5HPhH6.

The phase transitions, crystallization kinetics and molecular dynamics of (S)-4'-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy)pent-1-oxy] benzoate (3F5HPhH6) are investigated by differential scanning calorimetry, polarizing optical microscopy and broadband dielectric spectroscopy. The vitrification of the antiferroelectric hexatic phase is observed for cooling rates ≥5 K min-1 and the fragility index determined from dielectric data is mf ≈ 90. Two regimes of non-isothermal cold crystallization are distinguished using the Kissinger and Augis-Bennett methods in the heating rate ranges of 1-5 K min-1 (larger activation energy) and 8-20 K min-1 (lower activation energy). The correlation between the time of non-isothermal cold crystallization (using isothermal approximation) and relaxation time of the α-process is determined. The obtained coupling coefficient ξ ≈ 0.7 and temperature dependence of the crystallization rate Z from the Ozawa model imply a mainly diffusion-controlled cold crystallization below 275 K. The Avrami exponents n and Ozawa exponents nO determined for isothermal melt crystallization and non-isothermal cold crystallization, respectively, weigh in favour of two- rather than three-dimensional crystal growth. The transition between crystal phases is observed on heating, with a lower activation energy for 1-3 K min-1 than for 5-20 K min-1 rates.

Effect of high pressure on relaxation dynamics and crystallization kinetics of chiral liquid crystal in its smectic phase.

The impact of high pressure on molecular dynamics and the crystallization process in the smectic phase with antiferroelectric properties of partially fluorinated liquid crystal (S)-4'-(1-methyloctyloxycarbonyl)biphenyl-4-yl-4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy)heptyl-1-oxy]-benzoate (3F7HPhH7) was studied by broadband dielectric spectroscopy (BDS). By analyzing dielectric spectra measured under isobaric and isothermal conditions, the changes of the activation volume vs. temperature and the activation enthalpy vs. pressure have been determined to better understand the molecular system's behaviour in terms of its thermodynamic properties. The isothermal and isobar crystallization was studied by a BDS method along the trajectory of constant relaxation time τ on the (T, p) plane. The kinetics of this process was compared to that at ambient pressure, derived from the results of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The melt crystallization depends primarily on the formation of nuclei with the activation energy of approx. 50 kJ mol-1. This energy corresponds with the intramolecular movements of the carbonyl group in the rigid core. The behaviour of the apparent activation energies suggests that this process becomes easier with the progressive crystallized volume fractions. The obtained values of the Avrami exponent nA suggest that the crystal growth is three-dimensional. Additionally, we successfully used the scaling of dielectric response for experimental data. The scaling of the dielectric relaxation processes indicates that the dynamics and the behaviour of dielectric permittivity have the same origin for all phases regardless of the change in temperature and/or pressure.

Biological Performances of Plasmonic Biohybrids Based on Phyto-Silver/Silver Chloride Nanoparticles.

Silver/silver chloride nanoparticles (Ag/AgClNPs), with a mean size of 48.2 ± 9.5 nm and a zeta potential value of -31.1 ± 1.9 mV, obtained by the Green Chemistry approach from a mixture of nettle and grape extracts, were used as "building blocks" for the "green" development of plasmonic biohybrids containing biomimetic membranes and chitosan. The mechanism of biohybrid formation was elucidated by optical analyses (UV-vis absorption and emission fluorescence, FTIR, XRD, and SAXS) and microscopic techniques (AFM and SEM). The aforementioned novel materials showed a free radical scavenging capacity of 75% and excellent antimicrobial properties against Escherichia coli (IGZ = 45 mm) and Staphylococcus aureus (IGZ = 35 mm). The antiproliferative activity of biohybrids was highlighted by a therapeutic index value of 1.30 for HT-29 cancer cells and 1.77 for HepG2 cancer cells. At concentrations below 102.2 µM, these materials are not hemolytic, so they will not be harmful when found in the bloodstream. In conclusion, hybrid systems based on phyto-Ag/AgClNPs, artificial cell membranes, and chitosan can be considered potential adjuvants in liver and colorectal cancer treatment.

On the relaxation dynamics of a double glass-forming antiferroelectric liquid crystal.

The relaxation dynamics in the thermodynamic states of the glass-forming antiferroelectric liquid crystal (S)-4'-(1-methyloctyloxycarbonyl) biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-benzoate (3F7HPhH7) was studied by broadband dielectric spectroscopy (BDS). Two glass transitions were found at Tg,1 = 259 K and Tg,2 = 239 K, which were associated with the freezing of anti-phase motions and reorientation around the long molecular axis in the antiferroelectric SmCA* phase, respectively. The low temperature α2-relaxation process shows a Vogel-Fulcher-Tammann (VFT)-type temperature dependence of its structural relaxation time τ(T). The two secondary ß- and γ-relaxation modes ascribed to the intramolecular motions observed in the glassy state show Arrhenius behaviour of τ(T). Analysing the band shifts and the oscillator strengths of specific IR absorption bands and their temperature dependencies enables comparing them with the dielectrically determined relaxation dynamics. The kinetics of the isothermal cold crystallization in the temperature range between Tg,1 and Tg,2 was studied in detail using the Avrami and Avrami-Avramow models. This process depends primarily on the diffusion rate and the activation energy is equal to 132 kJ mol-1. The obtained values of the Avrami exponent nA suggest that the crystal growth is three-dimensional.

Vibrational Dynamics of Carbamazepine: Studies Based on Two-Dimensional Correlation Spectroscopy and X-ray Diffraction.

Fourier transform infrared spectroscopy as well as X-ray diffraction (XRD) were employed to thoroughly study phase transitions taking place during heating-cooling-heating cycle of carbamazepine (CBZ), a well known and commonly used antiepileptic drug. Both techniques revealed cold crystallization taking place during second heating. Moreover, XRD studies for the first time proved the coexistence of CBZ (form I) and iminostilbene (product of the degradation of CBZ) after a heating-cooling cycle. Moving window two-dimensional correlation (MW 2D-COS) spectroscopy and two-dimensional correlation spectroscopy were shown to be effective tools to reveal phase sequences and to provide information about the order of sequential changes of bands' intensities during each phase transition, respectively.

Dynamics of Dimethylbutanols in Plastic Crystalline Phases by Field Cycling 1H NMR Relaxometry.

2,2-Dimethylbutan-1-ol (2,2-DM-1-B), 3,3-dimethylbutan-1-ol (3,3-DM-1-B), and 3,3-dimethylbutan-2-ol (3,3-DM-2-B) show a rich solid-state polymorphism, which includes one or more plastic crystalline phases (also referred to as orientationally disordered crystalline (ODIC) phases) and glass of the liquid or ODIC phases. In this work, the dynamics of the three isomeric alcohols was investigated in the liquid and plastic crystalline phases by fast field cycling 1H NMR relaxometry in the temperature range between 213 and 303 K. The analysis of the nuclear magnetic relaxation dispersion curves (i.e., longitudinal relaxation rate R1 vs 1H Larmor frequency) acquired for the different alcohols at different temperatures gave quantitative information on internal motions, overall molecular reorientations, and molecular self-diffusion. Self-diffusion coefficients were also determined in the liquid phase and in some ODIC phases of the samples from the trends of 1H R1 as a function of the frequency square root at low frequencies. Remarkable changes in the temperature trends of correlation times and self-diffusion coefficients were found at the transition between the liquid and the ODIC phase for 2,2-DM-1-B and 3,3-DM-1-B, and between ODIC phases for 3,3-DM-2-B, the latter sample showing a markedly different dynamic and phase behavior.

Interplay between Crystallization and Glass Transition in Nematic Liquid Crystal 2,7-Bis(4-pentylphenyl)-9,9-diethyl-9 H-fluorene.

This article presents the crystallization behavior and molecular dynamics of the supercooled nematic state of the newly synthesized liquid crystal 2,7-bis(4-pentylphenyl)-9,9-diethyl-9 H-fluorene (5P-EtFLEt-P5) studied by means of broadband dielectric spectroscopy (BDS). 5P-EtFLEt-P5 is a fragile glass-forming system with a high fragility parameter ( mf ≈ 121). The study compares the isothermal melt- and cold-crystallization processes at several selected temperatures Tc in the vicinity of the glass-transition temperature Tg (1.07 Tg ≤ T ≤ 1.17 Tg). Our findings reveal that at low temperatures, the crystallization of the Cr1 phase from the nematic melt state occurs more quickly than the cold crystallization. The dimensionality of the growing crystallites ( n) was found to be slightly higher for the cold- than for the melt-crystallization process, varying from n ∼ 5 to n ∼ 3 with increasing temperature. Our experimental results are discussed in terms of dynamic and thermodynamic properties of the material. The study also uses polarized optical microscopy to investigate the isothermal secondary cold crystallization (the formation of Cr2 from Cr1 upon heating), which is inaccessible by BDS measurements because of its very fast crystallization rates.

Glass Transition Dynamics and Crystallization Kinetics in the Smectic Liquid Crystal 4-n-Butyloxybenzylidene-4'-n'-octylaniline (BBOA).

The molecular dynamics of 4-n-butyloxybenzylidene-4'-n'-octylaniline (BBOA, abbreviated also as 4O.8) was studied by broadband dielectric spectroscopy (BDS) for samples that were exposed to various thermal treatments. Phase transitions between liquid crystalline phases (N, SmA, SmBhex, and SmBCr) were evidenced by abrupt changes in the temperature dependence of the dielectric permittivity spectra and dielectric relaxation times. A particularly complex dynamic behavior was revealed for the highly ordered SmBCr phase that showed clear evidence for cooperative dynamics of a glass-forming liquid as manifested by a Vogel-Fulcher-Tammann (VFT)-type temperature dependence of its structural relaxation time τ(T). At low temperatures, dependence τ(T) again changes from VFT to Arrhenius behavior, a phenomenon commonly observed for supercooled liquids confined to nanometer length scales and occasionally discussed as strong-fragile transition on heating. In this context, our observation supports the idea of partial orientation disorder in a quenched SmBCr phase, where the length scale of cooperative motions is restricted to the nanometer size of glassy domains causing the deviation from "bulk" VFT-type behavior. Finally, the isothermal crystallization kinetics of the metastable SmBCr phase was studied in detail. On the basis of structural information about the SmBhex and SmBCr phases, determined by X-ray diffraction, the subtle relation between molecular order and relaxation behavior is discussed.

Dynamics of the Chiral Liquid Crystal 4'-Butyl-4-(S)-(2-methylbutoxy)azoxybenzene in the Isotropic, Cholesteric, and Solid Phases: A Fast Field-Cycling NMR Relaxometry Study.

(1)H NMR relaxometry was applied to investigate dynamic processes in the isotropic liquid, cholesteric, and crystalline phases of the chiral mesogen 4'-butyl-4-(S)-(2-methylbutoxy)azoxybenzene (4ABO5*). To this aim, (1)H longitudinal relaxation rates were measured as a function of temperature (between 257 and 319 K) and Larmor frequency (from 10 kHz to 35 MHz by a fast field-cycling relaxometer and at 400 MHz by an NMR spectrometer). The NMR relaxation dispersion (NMRD) curves so obtained were analyzed in terms of models suitable for the description of dynamic processes in the different phases, thus quantitatively determining values of characteristic motional parameters. In particular, internal and overall rotations/reorientations, molecular translational diffusion, and collective motions contribute to relaxation in the isotropic and cholesteric phases, whereas, in the crystalline phase, relaxation is mainly determined by internal motions and molecular reorientations. The results were discussed and compared with those previously obtained on the same compound by dielectric relaxation spectroscopy.

Tuning of Charge Transfer Assisted Phase Transition and Slow Magnetic Relaxation Functionalities in {Fe(9-x)Co(x)[W(CN)8]6} (x = 0-9) Molecular Solid Solution.

Precisely controlled stoichiometric mixtures of Co(2+) and Fe(2+) metal ions were combined with the [W(V)(CN)8](3-) metalloligand in a methanolic solution to produce a series of trimetallic cyanido-bridged {Fe(9-x)Co(x)[W(CN)8]6(MeOH)24}·12MeOH (x = 0, 1, ..., 8, 9; compounds 0, 1, ..., 8, 9) clusters. All the compounds, 0-9, are isostructural, and consist of pentadecanuclear clusters of a six-capped body-centered cube topology, capped by methanol molecules which are coordinated to 3d metal centers. Thus, they can be considered as a unique type of a cluster-based molecular solid solution in which different Co/Fe metal ratios can be introduced while preserving the coordination skeleton and the overall molecular architecture. Depending on the Co/Fe ratio, 0-9 exhibit an unprecedented tuning of magnetic functionalities which relate to charge transfer assisted phase transition effects and slow magnetic relaxation effects. The iron rich 0-5 phases exhibit thermally induced reversible structural phase transitions in the 180-220 K range with the critical temperatures being linearly dependent on the value of x. The phase transition in 0 is accompanied by (HS)Fe(II) W(V) ↔ (HS)Fe(III) W(IV) charge transfer (CT) and the additional minor contribution of a Fe-based spin crossover (SCO) effect. The Co-containing 1-5 phases reveal two simultaneous electron transfer processes which explore (HS)Fe(II) W(V) ↔ (HS)Fe(III) W(IV) CT and the more complex (HS)Co(II) W(V) ↔ (LS)Co(III) W(IV) charge transfer induced spin transition (CTIST). Detailed structural, spectroscopic, and magnetic studies help explain the specific role of both types of CN(-)-bridged moieties: the Fe-NC-W linkages activate the molecular network toward a phase transition, while the subsequent Co-W CTIST enhances structural changes and enlarges thermal hysteresis of the magnetic susceptibility. On the second side of the 0-9 series, the vanishing phase transition in the cobalt rich 6-9 phases results in the high-spin ground state, and in the occurrence of a slow magnetic relaxation process at low temperatures. The energy barrier of the magnetic relaxation gradually increases with the increasing value of x, reaching up to ΔE/kB = 22.3(3) K for compound 9.

Optical Activity and Dehydration-Driven Switching of Magnetic Properties in Enantiopure Cyanido-Bridged Co(II)3W(V)2 Trigonal Bipyramids.

The unique enantiopure {[Λ-Co(II)((R)-mpm)2]3[W(V)(CN)8]2}·9H2O [(R)-1] and {[Δ-Co(II)((S)-mpm)2]3[W(V)(CN)8]2}·9H2O [(S)-1], where mpm = α-methylpyridinemethanol, magnetic spongelike materials, crystallizing in the chiral P21 space group, are constructed of cyanido-bridged {Co3W2} trigonal bipyramids with three cis-[Co(II)(mpm)2(µ-NC)2] moieties in equatorial sites and two [W(V)(CN)8](3-) units in apical positions. The arrangement of {Co3W2} clusters in the crystal lattice is controlled by interactions with crystallization H2O molecules, resulting in two independent hydrogen-bonding systems: the first weaving along open channels in the a direction (weakly bonded H2O) and the second closed in the cages formed by the surrounding [W(CN)8](3-) and mpm fragments (strongly bonded H2O). The strong optical activity of (R)- and (S)-1 together with continuous chirality measure (CCM) analysis confirms the chirality transfer from enantiopure (R)- and (S)-mpm to [Co(mpm)2(µ-NC)2] units, a cyanido-bridged skeleton, and to the whole crystal lattice. Magnetic properties confronted with ab initio calculations prove the ferromagnetic couplings within Co(II)-NC-W(V) linkages inside {Co3W2} molecules, accompanied by weak antiferromagnetic intermolecular interactions. The reversible removal of weakly bonded H2O above 50 °C induces the structural phase transition 1 ⇄ 1deh and strongly affects the magnetic characteristics. The observed changes can be interpreted in terms of the combined effects of the decreasing strength of ferromagnetic Co(II)-W(V) coupling and the increasing role of antiferromagnetic intermolecular correlation, both connected with dehydration-induced structural modifications in the clusters' core and supramolecular network of 1.