Structure–Properties Relations in Werner β-[Ni(NCS)2(4-MePy)4] Clathrates. Part 2. Host–Host Interactions as a Function of the Guest Molecular Size and Shape and the Amount of Absorbed Guest Compound

Careful analysis of changes in the geometry of the host lattice structure on inclusion of different guest molecules was performed for 11 -[Ni(NCS)₂(4-methylpyridine)₄] clathrates reported in the literature, and specific features were established for the geometry of the host crystal lattice structure, which are characteristic for different modes of location of the guest molecules. A new method is suggested for the analysis of the volume and shape of the empty space in clathrates. Experimental data are reported on the dependence of the a and c parameters of the unit cell of clathrate phases (with furan and dichloromethane as guest components) from the guest uptake. Consideration of these data permit us to construct a model of the changes of host–host interactions in the -[Ni(NCS)₂(4-methylpyridine)₄] clathrates with change of guest uptakes. Modeling of the process of diffusion of the guest molecule through the channel of the -[Ni(NCS)₂(4-methylpyridine)₄] clathrate allowed the nature of the rate-determining step of diffusion to be established. Part 1 of this series has been published as [3].     

Simulations of Guest Transport in Clathrates of Dianin’s Compound and Hydroquinone

Clathrates have been proposed for use in a variety of applications including gas storage, mixture separation and catalysis due to the potential for controlled guest diffusion through their porous lattices. Here molecular dynamics simulations are employed to study guest transport in clathrates of hydroquinone (HQ) and Dianin’s compound (DC). Systems investigated were HQ with methanol and acetonitrile, and DC with methanol and ethanol. Simulations were set up with one guest in the pore, two guests in the pore and one vacancy in the pore and a filled pore, and free‐energy barriers for movement between cavities of the pore were estimated for all cases. Comparison between these simulations indicates that guest transport most likely proceeds by molecules moving from full to empty cavities consecutively, one by one, rather than in a concerted manner. Thus, the presence of empty cavities is very important for guest transport, which becomes more energetically demanding in fully loaded systems. Flexibility of the host can assist guest transport. In the studied DC clathrates transport occurs via an intermediate conformation in which the hydroxyl group of the alcohol guest molecule participates in the hydrogen‐bonded ring of the host. We also address the issue of the number of methanol guest molecules that DC accommodates, for which conflicting information exists. We found that this is likely to be temperature dependent and suggest that under some conditions the system is most likely non‐stoichiometric.     

Phase and orientational ordering of low molecular weight rod molecules in a quenched liquid crystalline polymer matrix with mobile side chains

We study the phase diagram and orientational ordering of guest liquid crystalline (LC) rods immersed in a quenched host made of a liquid crystalline polymer (LCP) matrix with mobile side chains. The LCP matrix lies below the glass transition of the polymer backbone. The side chains are mobile and can align to the guest rod molecules in a plane normal to the local LCP chain contour. A field theoretic formulation for this system is proposed and the effects of the LCP matrix on LC ordering are determined numerically. We obtain simple analytical equations for the nematic/isotropic phase diagram boundaries. Our calculation show a nematic-nematic (N/N) first order transition from a guest stabilized to a guest-host stabilized region and the possibility of a reentrant transition from a guest stabilized nematic region to a host only stabilized regime separated by an isotropic phase. A detailed study of thermodynamic variables and interactions on orientational ordering and phases is carried out and the relevance of our predictions to experiments and computer simulations is presented.     

Structural and Dynamical Properties of n-Alkane Molecules in Clathrate Phase of Syndiotactic Polystyrene

Syndiotactic polystyrene (sPS) forms a clathrate phase with a variety of compounds. Not only rigid molecules but also flexible molecules can be stored in the cavities of the clathrate phase. To clarify the adjustment mechanism of a flexible guest molecule to the sPS clathrate system, the host and guest structures were investigated by means of solid-state ¹³C NMR and Raman spectroscopy, and X-ray diffractometry for the sPS clathrates with a series of n-alkanes from n-hexane to n-decane. Although the 010 spacing of the host sPS lattice expanded slightly on going from n-hexane to n-heptane, it decreased markedly at n-octane and then increased gradually with the chain length of guest n-alkane. The conformational change of guest n-alkane molecules was involved in this anomalous change in the 010 spacing. Majority of the n-hexane and n-heptane molecules took extended chain structures in the clathrates, whereas all longer n-alkanes took bent chain structures. The mean-square displacement of hydrogen atoms in the clathrates was estimated by quasielastic neutron scattering experiments. It was confirmed that the host lattice contraction suppressed thermal motion of the clathrate system.     

Probing structural transition and guest dynamics of hydroquinone clathrates by temperature-dependent terahertz time-domain spectroscopy

The structural transition from hydroquinone clathrates to crystalline α-form hydroquinone was observed up to the range of 3 THz frequency as a function of temperatures. We found that all three hydroquinone clathrates, CO(2)-, CH(4)-, and CO(2)/CH(4)-loaded hydroquinone clathrates, transform into the α-form hydroquinone at around 102 ± 7 °C. The resonance peak of the CO(2)-loaded hydroquinone clathrate at 2.15 THz decreases with increasing temperature, indicating that CO(2) guest molecules are readily released from the host framework prior to the structural transformation. This reveals that the hydroquinone clathrates may transform into the stable α-form hydroquinone via the metastable form of guest-free clathrate, which depends on guest molecules enclathrated in the cages of the host frameworks. A strong resonance of the α-form hydroquinone at 1.18 THz gradually shifts to the low frequency with increasing temperature and shifts back to the high frequency with decreasing temperature.     

Stoichiometry of clathrates

Two aspects of clathrate stoichiometry are discussed: structural stoichiometry and variation in composition due to variable occupation of host cavities in the framework by guest molecules. The solid solutions that are due to the variable occupation of cavities (iskhoric solutions) are classified into two types according to the stability of the hollow clathrate framework of the host. The first type involves compounds with stable hollow frameworks (the occupancies change from zero), and the second type are compounds with metastable hollow frameworks (the occupancies change from certain positive values). Special attention is paid to a wide class of clathrate compounds of constant composition (currently all clathrates are regarded as nonstoichiometric compounds). Clathrates of constant composition are formed when the hollow framework of the host is absolutely unstable. Reasons for instability of the frameworks are discussed, and theoretical models designed on the basis of the available data are considered. Examples of alloxenic (with one guest replaced by another) and allokiric (with replacements in the host subsystem) solid clathrate solutions are given. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Struktumoi Khimii, Vol. 36, No. 6, pp. 1088–1141, November–December, 1995. Translated by L. Smolina     

Structural investigations and modeling of cavities in clathrates

Summary A molecular-graphics study has been performed in order to build and visualize the shape of cavities within different clathrates from X-ray diffraction data [e.g. Dianin's compound, Werner complexes Ni(SCN)₂(3-methylpyridine)₄, Fe(acetylacetonate)₃ and Ni(ethylxanthate)₂(4,4-dimethyl-2,2-bipyridyl) complexes]. The algorithm of the solvent-accessible surfaces representation has been applied to a part of the whole crystal structure rather than to isolated host molecules, by using the MOLCAD molecular modeling package. This type of modelization has been found very efficient both to study the shape properties of the host cavities (cage or channel types) and to approach the structural features of the host/guest interactions.     

Clathrate formation and phase transitions in β-hydroquinone

Clathrate thermodynamic stability conditions and the phase transitions associated with either the orientational ordering of the guest molecules or with the condensation of the guest molecules in the host lattice are investigated by means of the common microscopic model. The theory proposed describes the thermodynamic properties of -hydroquinone (Q ) clathrates. The dielectric constant (T) was measured experimentally inQ ·CH₃OH andQ ·SO₂ in the temperature range from 4.2 to 300 K and the phase transitions were found. It is shown that the theory qualitatively explains the experimental data obtained.Dedicated to Professor H. M. Powell.     

Temperature-dependent crystal structure of the isopropanol clathrate of Dianin's compound

The title compound undergoes two order-disorder transitions between 15 and 299 K, dictated by ordering of the guest molecules in the host cages, and resulting in three related crystal structures. We anticipate behaviour of this kind to be widespread, and speculate that the concept of "the crystal structure" for individual Dianin's clathrates may be elusive.     

Structure-property relationship for clathrates formed in systems with guest vapor and 1,3-disubstituted <Emphasis Type="Italic">tert</Emphasis>-butylcalix[4]arene

Structure-property relationship was studied for a series of clathrates formed in the systems that model guest-host interactions on the surface of chemical odor sensors of quartz microbalance type. The clathrates of 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis(2-naphthylmethoxy)calix[4]arene (1) obtained by the saturation of its powder with gaseous organic compounds (guests) with the unity thermodynamic activity at 298 K were studied. The stoichiometry and temperature at the starting and ending points of thermal dissociation were determined for all the clathrates and stable intermediates by thermal gravimetric analysis. A sorption isotherm was determined for one guest-host combination; it indicates the formation of a stable clathrate in the system and phase transition of host upon reacting with guest. Decrease in thermal stability of the clathrates of 1 with guests of greater size was observed for studied pairs of homologous guests.     

An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl)

Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)₄G (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates.     

Clathrate inclusiom compounds of bis(isothiocyanato) tetrakis (4-methylpyridine) nickel II: II. Arrangement of guest molecules in the β-Ni(NCS)2(4-methylpyrldine)4 porous crystals

In this paper crystal structures of three tetragonal 14₁/a β-Ni(NCS)₂(4-Methylpyridine)₄ clathrates containing p-xylene (1:1), m-xylene (1:1) and methanol (2:1 mole of guest/mole of host), respectively, as the guest components are reported and discussed.The guest molecules were found to occupy centrosymmetric cavities in the hoat structure. Non-centrosymmetric m-xylene molecules are disordered to at least two orientations interrelated by inversion; methanol molecules enter the cavities as centrosymmetric pairs.     

New crystal structures of β-[Ni(NCS)2(4-methylpyridine)4] clathrates with furan,tetrahydrofuran, methylene chloride,benzene + ethanol and methylcellosolve as guest molecules

Single crystal X-ray structures of clathrates of -[Ni(NCS)₂(4-methylpyridine)₄] with furan, tetrahydrofuran, benzene + ethanol, methylene chloride, and methylcellosolve as guests molecules are reported. The location of the guest molecule in the partially decomposed clathrate with methylene chloride was defined by X-ray diffraction and compared with the fully occupied one. The host lattices of all clathrates studied are tetragonal (I4₁/a) and do not differ significantly from typical -phase clathrates of [M(NCS)₂(4-methylpyridine)₄] (M = divalent metal cation). Arrangements of guest molecules represent different types of packing: one type of guest molecule occupies both possible types of positions, two different guest molecules occupy different positions, with only one type of positions occupied by one type of guest molecule. Possible stoichiometries of clathrates with -type lattices are discussed.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August 1995.     

Heterogeneous asymmetric ring-opening reactions of prochiral epoxides included as guest molecules in tri-o-thymotide clathrates.

Enantiomorphous tri-o-thymotide clathrates of prochiral oxiranes were submitted to the action of gaseous hydrogen halides. Ring-opening reactions ensued that differ from those reported in homogeneous phase, showing a considerable modification of the chemical reactivity of the external reagent in the host lattice. Chirality transfer from the host receptors to the guest products was also observed, but with a poor efficiency.     

Host/Guest Chemistry of Organic Onium Compounds—Clathrates,Crystalline Complexes,and Molecular Inclusion Compounds in Aqueous Solution

The importance of organic onium compounds for host/guest interactions in biological processes has been long recognized. In contrast, the versatility of synthetic onium compounds as host molecules in abiotic chemistry has only been investigated in detail for the last few years. Due to their inclusion ability and selectivities, organic ammonium, pyridinium, and phosphonium salts and other organic salts with specific structural features are interesting as clathrate-forming molecules. The crystal structures of the clathrates afford insight into the conformational adaptability of onium clathrands with limited flexibility to the geometric requirements of the guest molecules. Optically active onium hosts can be used for enantiomeric enrichment. In crystalline tetracyanoquinodimethane(TCNQ) complexes and radical anion salts, the structure of the organic heterocation has a marked effect on the electrical conductivity. Macrocyclic onium compounds of the phane type with “exohydrophilic” and “endolipophilic” cavities are suitable as models of enzymes and biological receptors. They can also be used to transfer aromatic and aliphatic guest molecules selectively into aqueous solution. Catalytic activity (including H/D exchange) has already been obtained with synthetic compounds having large cavities. The further development of such host/guest systems may contribute to the understanding of biological systems and the improvement of technical processes (catalysis in molecular cavities).     

Far-infrared spectra of some β-hydroquinone clathrates

Far-infrared spectra (400-30 cm^?1) of Nujol mulls of the β-hydroquinone clathrates containing the following guest molecules were investigated: formic acid, formic acid-d₂, methanol, methanol-d₄, acetonitrile, acetonitrile-d₃, sulphur dioxide and also both of methanol and sulphur dioxide. The observed infrared bands of the mulls in the region of 4000-30 cm^?1 were classified into those due to the host lattice and those due to the guest molecules. On the basis of the comparison of the spectra, some bands were assigned to the translational or the rotational vibrations of guest molecules. Appearance of those bands suggested that some guest molecules are considerably bound in the cavities of the host lattice. Effect of temperature change on the bands was also measured.     

Infrared Spectroscopic Study of the Hofmann-daon-Type Clathrates : M(1,8-diaminooctane)Ni(CN)4⋅G (M=Co, Ni or Cd; G=Aromatic Guest Molecules)

Infrared spectra of M(1,8-diaminooctane)Ni(CN)4G (M= Co, Ni or Cd; G=benzene, chlorobenzene, toluene, p-xylene, naphthalene or biphenyl) compounds are reported. The 1,8-diaminooctane molecules in the host permit the inclusion of bulky guest molecules. The spectral features suggest that the compounds are similar in structure to the Hofmann-type clathrates.     

Adsorption-induced structural transition of an interpenetrated porous coordination polymer: detailed exploration of free energy profiles

Specific types of coordination polymers show an adsorption-induced structural transition, or so-called "gate adsorption", in which a host framework is said to change its structure from a "closed" nonporous phase to an "open" porous one for guest molecules. To identify the pathway for such a structural transition, we perform grand canonical Monte Carlo simulations for the adsorption of guest molecules in a host interpenetrated framework and calculate the free energy profiles of the structural changes in a complete three-dimensional space. In addition to the open phase found in our previous analyses along a fixed one-dimensional path, we reveal the existence of another open configuration. Each of the two open phases yields the status of global minimum to the other depending on the external pressure, resulting in a two-step isotherm. Moreover, the shape of adsorption hysteresis associated with the structural transition can change depending on the energy barrier between a metastable and a stable state that the system can overcome. Our simulations not only give a comprehensive understanding of stepped isotherms observed empirically but also suggest that isotherms with hysteretic gate adsorption is closely related to the thermal fluctuation of the system.     

Clathrate and inclusion compounds. Part 8 [1]. An investigation of the usefulness of the spectral substraction technique in analysing the infrared spectra of clathrates

An investigation has been carried out into the usefulness of the spectral subtraction technique in analyzing the infrared spectra of the clathrates of quinol and of Dianin's compound. Due to the flexibility of the quinol host lattice, it is not advisable to use guest-free -quinol as the reference if the host lattice in the clathrate is considerably distorted, as it is in the CH₃CN clathrate. In this case it is advisable to use another clathrate as the reference provided that the spectrum of the new reference does not contain guest bands in the region of interest. The Dianin's compound host lattice is less flexible than that of quinol, and guest-free Dianin's compound can be used as the reference irrespective of the size of the guest molecule. With both clathrates the spectral subtraction technique has revealed guest molecule bands which were previously obscured by host lattice bands.Dedicated to Professor H. M. Powell.