Blends of amphiphilic trisilanolisobutyl-POSS and phosphine oxide substituted poly(dimethylsiloxane) at the air/water interface

Mixtures of a polyhedral oligomeric silsesquioxane, trisilanolisobutyl-POSS, and a polar silicone, poly(dimethyl-co-methylvinyl-co-methyl, 2-diphenyl phosphine oxide ethyl) siloxane (PDMS-PO), spread as Langmuir monolayers at the air/water interface are used to examine the surface phase behavior and aggregation of trisilanolisobutyl-POSS as a function of silicone composition. Analyses of the surface pressure-area per monomer (Pi-A) isotherms in terms of the collapse pressures and excess Gibbs free energies of mixing indicate the monolayers form slightly negative deviation mixtures. Direct observations of surface morphology with Brewster angle microscopy in the collapsed regime reveal that the governing factor for aggregation is the collapse Pi of the component with a stronger affinity for water. In trisilanolisobutyl-POSS/PDMS-PO blends, POSS aggregates as discrete domains and does not coalesce into larger aggregates or networklike structures for <80 wt % POSS, a feature that is vastly different from a previous study of POSS blended with regular poly(dimethylsiloxane).     

Motion of an isolated water molecule within a flexible coordination cage: structural properties and catalytic effects of ionic palladium(II) complexes

The unique cage complexes [[(Me(4)en)Pd](3)(L)(2)](X)(6) (L = 1,3,5-tris(isonicotinoyloxyethyl)cyanurate; X(-) = BF(4)(-), ClO(4)(-)) were constructed. A single water molecule in a skeletal cage was reversibly associated and dissociated via a combination of the adequate space, polar environment, and conformational flexibility of the cage. In Suzuki-Miyaura C-C cross-coupling reactions, the cage complex showed significant catalytic activity along with the effects of the isolated single water molecule.     

Blends of amphiphilic poly(dimethylsiloxane) and nonamphiphilic octaisobutyl-POSS at the air/water interface

Brewster angle microscopy (BAM) shows that a nonamphiphilic polyhedral oligomeric silsesquioxane (POSS) nanofiller, octaisobutyl-POSS, forms aggregates at all surface concentrations at the air/water interface. When amphiphilic poly(dimethylsiloxane) (PDMS) is blended with the octaisobutyl-POSS (>10 wt % PDMS), the degree of POSS aggregation dramatically decreases. Thermodynamic analyses and morphology studies through surface pressure-area per monomer isotherm data and BAM, respectively, exhibit three distinct composition regimes: (1) Blends with >70 wt % POSS have unstable isotherms whose shapes deviate from those of PDMS and form large rigid domains comparable to but smaller than pure, octaisobutyl-POSS films. (2) At compositions between approximately 40 and 70 wt % POSS, the isotherms' features are qualitatively similar to those of pure PDMS, and extensive nanofiller "networks" are observed by BAM. (3) For compositions < or = approximately 30 wt % POSS, the isotherms are essentially those of pure PDMS with small POSS domains dispersed in the PDMS matrix. These results provide further insight into nanofiller aggregation mechanisms and dispersion that may be present in thicker films and bulk systems.     

Vibronic dynamics of I(2) trapped in amorphous ice: coherent following of cage relaxation

Four-wave mixing measurements are carried out on I(2)-doped ice, prepared by quench condensing the premixed vapor at 128 K. Coherent vibrational dynamics is observed in two distinct ensembles. The first is ascribed to trapping in asymmetric polar cages in which, as in water, the valence absorption of the molecule is blueshifted by 3500 cm(-1), predissociation of the B state is complete upon the first extension of the molecular bond, and the vibrational frequency in the ground state (observed through coherent anti-Stokes Raman scattering) is reduced by 6.5%. The effect is ascribed to polarization of the molecule. The implied local field and the ionicity of the molecule are extracted, to conclude that the molecule is oxygen bonded to one water molecule on one side and hydrogen bonded on the other side. The second ensemble is characterized by the transient grating signal, which shows coherent vibrational dynamics on the B state. The small predissociation rate in this site suggests a symmetric cage in which the local electric field undergoes effective cancellation; and consistent with this, the extracted blueshift of the valence transition in this site (approximately 1500 cm(-1)) coincides with that observed in clathrate hydrates of iodine. Remarkably, in this site, the vibrational period of the B state packet coherently stretches from an initial value of 245 fs to 325 fs in the course of five oscillations (1.3 ps), indicative of vibrationally adiabatic following of the cage expansion. The dynamics is characteristic of a molecule trapped in a tight symmetric cage, with a soft cage coordinate that relaxes without eliciting elastic response. Enclathration in low-density amorphous ice is concluded.     

N60的量子化学研究

C60的发现及其广泛研究促使人们去探索合成其它元素的笼形化合物，特别是氮笼分子，被认为具有较高的热值，是潜在的高能密度材料（HEDM）］，尤其是将其作为火箭推进剂时，可通过自身的分解释放能量，并产生叱，不需要携带供氧物质，这对火箭推进剂的研制将带来根本性的变革，因此倍受人们重视．日本曾在“老任新阁”中简单地提到他们对N。。进行了计算，得到的构型是有几个向内凹陷的宪状体，但对具体的计算结果尚未见报道．本文报道了N60的计算方法及结果．1计算方法计算系采用Turbomole程序，在SGI／ONYXI作站上进行．利用HF从…     

One and two hydrogen molecules in the large cage of the structure II clathrate hydrate: quantum translation-rotation dynamics close to the cage wall

We have performed a rigorous theoretical study of the quantum translation-rotation (T-R) dynamics of one and two H2 and D2 molecules confined inside the large hexakaidecahedral (5(12)6(4)) cage of the sII clathrate hydrate. For a single encapsulated H2 and D2 molecule, accurate quantum five-dimensional calculations of the T-R energy levels and wave functions are performed that include explicitly, as fully coupled, all three translational and the two rotational degrees of freedom of the hydrogen molecule, while the cage is taken to be rigid. In addition, the ground-state properties, energetics, and spatial distribution of one and two p-H2 and o-D2 molecules in the large cage are calculated rigorously using the diffusion Monte Carlo method. These calculations reveal that the low-energy T-R dynamics of hydrogen molecules in the large cage are qualitatively different from that inside the small cage, studied by us recently. This is caused by the following: (i) The large cage has a cavity whose diameter is about twice that of the small cage for the hydrogen molecule. (ii) In the small cage, the potential energy surface (PES) for H2 is essentially flat in the central region, while in the large cage the PES has a prominent maximum at the cage center, whose height exceeds the T-R zero-point energy of H2/D2. As a result, the guest molecule is excluded from the central part of the large cage, its wave function localized around the off-center global minimum. Peculiar quantum dynamics of the hydrogen molecule squeezed between the central maximum and the cage wall manifests in the excited T-R states whose energies and wave functions differ greatly from those for the small cage. Moreover, they are sensitive to the variations in the hydrogen-bonding topology, which modulate the corrugation of the cage wall.     

Theoretical study on the molecule C30H20: five carbon–carbon single bonds linking a dodecahedrane cage and a pentaprismane cage

Using geometry optimization and DFT method at the B3LYP/6-31G* level of theory for C₃₀H₂₀, an equilibrium geometry is identified that has the form of polyhedral hydrocarbon with five carbon–carbon single bonds linking a dodecahedrane cage and a pentaprismane cage. Thus, this molecule is a tri-cage molecule with two pentaprismane cages and one dodecahedrane cage. Vibrational frequencies and the infrared spectrum are computed at the same level of theory. The heat of formation for C₃₀H₂₀ has been estimated in this paper. The heat of formation of C₃₀H₂₀ as well as the vibrational analysis indicates that this molecule enjoys sufficient stability to allow for its experimental preparation.     

Vibrational relaxation of oxygen in an argon cage

The vibrational relaxation of oxygen embedded in an argon cage through vibrational to local translation, rotation, and argon phonon modes has been studied using semiclassical procedures. The collision model is based on the trapped molecule undergoing the restricted motions (local translation and hindered rotation) in a cage formed by its twelve nearest argon neighbors in a face-centered-cubic structure. At 85 K in the liquid argon temperature range, the deexcitation probability of O(2)(v=1) is 5.8 x 10(-12) and the relaxation rate constant with the collision frequency from local translation is 23 s(-1). The rate constant decreases to 5.1 s(-1) at 50 K and to 0.016 s(-1) at 10 K in the solid argon temperature range. Transfer of the vibrational energy to local translation, rotation (both hindered and free), and argon phonon modes is the relaxation pathway for the trapped oxygen molecule.     

5,6]-Heterofullerene-like C58Ge: odd atoms assembling a cage

Density functional calculations and structural minimization techniques have been employed to characterize the structural and electronic properties of [5,6]-heterofullerene-like C(58)Ge. The heterofullerene molecule has an odd number of atoms on the skeleton of the cage and is a novel molecule. The vibrational frequencies of the molecule have been calculated at the B3LYP/3-21G level of theory. The absence of imaginary vibrational frequency confirms that the molecule corresponds to a true minimum on the potential energy hypersurface. Its heat of formation was estimated in this study. Since the symmetry of the molecule of [5,6]-heterofullerene-like C(58)Ge is C(2), it is a chiral molecule.     

Electronic structure, molecular interaction, and stability of the CH4-nH2O complex, for n = 1-21

Molecular calculations were carried out with four different methodologies to study the CH 4- nH 2O complex, for n = 1-21. The HF and MP2 methods used considered the O atom with pseudopotential to freeze the 1s shell. The other methodologies applied the Bhandhlyp and B3lyp exchange and correlation functionals. The optimized CH 4- nH 2O structures are reported, specifying the number and type of H 2O subunits (triangle, square, pentagon, etc.) that comprised the nH 2O counterpart cluster or cage, that interacted with the CH 4 molecule, and, in the latter case, that provided its confinement. Results are focused to understand the stability of the CH 4- nH 2O complex. The quality of the electron correlation effect, as well as the size of the nH 2O cage to confine the guest molecule, and the number and type of H 2O subunits comprising the nH 2O cluster or cage are the most important factors to provide the stability of the complex and also dictate the particular n value at which the CH 4 molecule confinement occurs. This number was 14 for the HF, Bhandhlyp, and B3Lyp methods and 16 for the MP2 method. The reported hydrate structures for n < 20 could be predictive for future experiments.     

Highly CO2-selective organic molecular cages: what determines the CO2 selectivity

A series of novel organic cage compounds 1-4 were successfully synthesized from readily available starting materials in one-pot in decent to excellent yields (46-90%) through a dynamic covalent chemistry approach (imine condensation reaction). Covalently cross-linked cage framework 14 was obtained through the cage-to-framework strategy via the Sonogashira coupling of cage 4 with the 1,4-diethynylbenzene linker molecule. Cage compounds 1-4 and framework 14 exhibited exceptional high ideal selectivity (36/1-138/1) in adsorption of CO(2) over N(2) under the standard temperature and pressure (STP, 20 °C, 1 bar). Gas adsorption studies indicate that the high selectivity is provided not only by the amino group density (mol/g), but also by the intrinsic pore size of the cage structure (distance between the top and bottom panels), which can be tuned by judiciously choosing building blocks of different size. The systematic studies on the structure-property relationship of this novel class of organic cages are reported herein for the first time; they provide critical knowledge on the rational design principle of these cage-based porous materials that have shown great potential in gas separation and carbon capture applications.     

A neutral self-assembled coordination cage organized for inclusion of aromatic guests

Jahn-Teller distorted Cu2+ centers, axially ligated by RSO(3)(-) groups, act as spacers to form a cage molecule with ligands organized at a distance well-suited for inclusion of aromatics.     

An ab initio study of microsolvation of LiF in water: structures and properties of LiF-Wn,n = 1-9 complexes

Geometries of clusters of water molecules (W(n)) and those of the LiF-W(n) (n = 1-9) complexes were optimized using the B3LYP/6-31+G** method. Geometries of the complexes up to n = 7 were also optimized using the MP2/6-31+G** approach. Only one structure of each of W(n), n = 1-5 was considered to generate the complexes with LiF while two structures, one of a cage type and the other of a prism type, were considered for n = 6-9. The LiF-W(2) complex is found to be most stable among the various complexes. The LiF-W(6) complex, where W(6) is of a cage type, is predicted to be substantially less stable than that where W(6) is of a prism type. Certain existing ambiguities regarding the most stable structures of the LiF-W(n) (n = 1-3) complexes have been resolved. The LiF molecule seems to divide the W(n) clusters in the LiF-W(n) (n = 3-6) complexes into different fragments where at least one W(2)-like fragment is present. In LiF-W(6) (cage), there is one W(2)-like fragment while in LiF-W(6) (prism), there are three W(2)-like fragments. The LiF bond length is substantially increased in going from the gas phase to the different complexes, this increase being most prominent in LiF-W(6), where W(6) is of the cage or prism type. The LiF molecule, however, does not acquire the ionic structure Li(+)F(-) in any of the complexes studied here. An appreciable amount of electronic charge is transferred from LiF to the water molecules involved in the different complexes. In this process, the Li atom gains electronic charge in some cases, while the F atom considered separately, as well as the Li and F atoms taken together, lose the same in most cases.     

Oxa-bicyclocalixarenes: a new cage for anions via C-H...anion hydrogen bonds and anion...pi interactions

Density functional theory calculations indicate that the cage molecule 4 can trap F- in the gas phase (-80.5 kcal/mol) as well as in CH2Cl2 (-14.7 kcal/mol) via strong C-H...F- hydrogen bonds and pi...F- interaction.     

C80 encaging four different atoms: the synthesis, isolation, and characterizations of ScYErN@C80

The synthesis, isolation, and spectroscopic characterizations of an endohedral fullerene with four heteroatoms encapsulated (ScYErN@C80) are reported for the first time. The isomeric structure and electronic properties of this molecule are studied by various spectrometry methods such as high-performance liquid chromatography (HPLC), laser desorption time-of-flight (LD-TOF) mass spectroscopy, cyclic voltammetry, Fourier transform infrared (FTIR) spectroscopy, and visible-near infrared (vis-NIR) absorption spectroscopy. The carbon cage of ScYErN@C80 is assigned as Ih-C80, and the four-membered ScYErN cluster is suggested to rotate rapidly inside the fullerene cage. Six electrons are transferred from the nuclear cluster ScYErN to the fullerene cage, which leads to a closed-shell electronic structure of the Ih-C80 and results in excellent stability of this molecule.     

Polyhedral oligomeric silsesquioxane amphiphiles: isotherm and brewster angle microscopy studies of trisilanolisobutyl-POSS at the air/water interface

A trisilanol derivative of polyhedral oligomeric silsesquioxanes (POSS), trisilanolisobutyl-POSS, has recently been reported to form stable monolayers at the air/water interface. Moreover, the trisilanolisobutyl-POSS monolayer undergoes a nonequilibrium structural transition (collapse) around a surface pressure of Rho approximately 18 mN.m(-1). This paper explores the mono- and multilayer properties of POSS molecules at the air/water interface by the Wilhelmy plate technique and Brewster angle microscopy. Surface concentrations are controlled by four mechanisms: (1) compression at a constant rate, (2) stepwise compression followed by surface pressure relaxation to an "equilibrium" value, (3) successive additions of spreading solution followed by relaxation to a stable surface pressure value, and (4) hysteresis loops to test the reversibility of the structural transitions. Results show that both an increasing compression rate and a decreasing temperature lead to an increase in the surface pressure of the structural transition, which is consistent with the formation of solidlike multilayer domains during the collapse process. For the case of compression at a constant rate, small domains initially form and later aggregate to form large solid masses. Cessation of compression allows these large solid masses to relax into equilibrium ringlike structures with a lower surface pressure, Rho approximately 13 mN.m(-1). In contrast, if the film is expanded rapidly, these large solidlike domains relax into "spaghetti" like networks with a residual surface pressure that depends on the initial amount of the solidlike collapsed phase. Finally, successive addition and stepwise compression isotherm experiments lead to different and time-dependent morphologies. Understanding these surface properties of POSS molecules affords an excellent opportunity to design and study POSS/polymer blends for coating applications where POSS molecules with rigid inorganic cores, soft organic coronae, and dimensions comparable to polymeric monolayers can serve as perfectly monodisperse nanofillers.     

Self-assembly of frameworks with specific topologies: construction and anion exchange properties of M3L2 architectures by tripodal ligands and silver(I) salts

Three five-component architectures, compounds 3, 4, and 5 were obtained by self-assembly of tripodal 1,3,5-tris(imidazol-1-ylmethyl )-2,4,6-trimethylbenzene (6) and 1,3,5-tris(benzimidazol-2-ylmethyl)benzene (7) ligands with silver(I) salts. The structures of these novel complexes have been determined by X-ray crystallography. The results of structural analysis indicate that these frameworks have same M3L2 components, but different structures. Compounds 3 and 4 are both M3L2 type cage-like complexes, while the 5 is an open trinuclear complex. The complex 3 is a cylindrical cage with simultaneous inclusion of a perchlorate anion inside of the cage as a guest molecule. Such guests can be exchanged for other anions through the open edge of the cage as evidenced by crystal structure of 4. The results demonstrate that the molecular M3L2 type cage can act as a host for anions and provide a nice example of supramolecular architectures with interesting properties and possible applications.     

Vibrational relaxation of molecular ions at low temperatures: O2(-) (v=1) + Ar

The vibrational relaxation of oxygen molecular ions trapped in an argon cage in the temperature range 10-85 K has been studied using semiclassical procedures. The collision model is based on the trapped molecule undergoing the restricted motions (local translation and hindered rotation) in a cage formed by its 12 nearest argon neighbors in a face-centered cubic arrangement. At 85 K in the liquid argon temperature range, the relaxation rate constant of O2(-) (v=1) is 1130 s(-1). The rate constant decreases to 270 s(-1) at 50 K and to 3.90 s(-1) at 10 K in the solid argon temperature range. In the range 10-85 K, the rate constant closely follows the temperature dependence k proportional to T2.7. Energy transfer pathways for the trapped molecular ion are vibration to local translation, argon phonon modes, and rotation (both hindered and free).     

Hydrogen molecule in the small dodecahedral cage of a clathrate hydrate: quantum translation-rotation dynamics at higher excitation energies

Higher-lying five-dimensional translation-rotation (T-R) eigenstates of a single p-H2 and o-D2 molecule confined inside the small dodecahedral (512) cage of the structure II clathrate hydrate are calculated rigorously, as fully coupled, with the cage assumed to be rigid. The calculations cover the excitation energies up to and beyond the j=2 rotational level of the free molecule, 356 cm(-1) for H2 and 179 cm(-1) for D2. It is found that j is a good quantum number for all the T-R states of p-H2, j=0 and j=2, considered. The same is not true for o-D2, where a number of T-R states in the neighborhood of the j=2 level show significant mixing of j=0 and j=2 rotational basis functions. The 5-fold degeneracy of the j=2 level of p-H2 is lifted completely due to the anisotropy of the cage environment, as is the 3-fold degeneracy of the j=1 level of o-H2 studied by us previously. Pure translational mode excitations with up to four quanta display negative anharmonicity, which was observed earlier for the translational fundamentals and their first overtones. The issues of assigning the combination states of p-H2 with excitations of two or all three translational modes, and of the strength of the mode coupling as a function of the excitation energy, are studied carefully for a range of quantum numbers. The average T-R energy of the encapsulated p-H2 is calculated as a function of temperature from 0 to 150 K.     

Studies on the encapsulation of various anions in different fullerenes using density functional theory calculations and Born-Oppenheimer molecular dynamics simulation

The density functional theory (DFT)-based Becke's three parameter hybrid exchange functional and Lee-Yang-Parr correlation functional (B3LYP) calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations have been performed to understand the stability of different anions inside fullerenes of various sizes. As expected, the stability of anion inside the fullerene depends on its size as well as on the size of the fullerene. Results show that the encapsulation of anions in larger fullerenes (smaller fullerene) is energetically favorable (not favorable). The minimum size of the fullerene required to encapsulate F(-) is equal to C(32). It is found from the results that C(60) can accommodate F(-), Cl(-), Br(-), OH(-), and CN(-). The electron density topology analysis using atoms in molecule (AIM) approach vividly delineates the interaction between fullerene and anion. Although F(-)@C(30) is energetically not favorable, the BOMD results reveal that the anion fluctuates around the center of the cage. The anion does not exhibit any tendency to escape from the cage.