Close-packed Research Articles

Highly Efficient Multiphoton Absorption of Zinc-AIEgen Metal-Organic Frameworks.

A series of luminescent frameworks was synthesized from the selective combination of aggregation induced emission (AIE)-linker tetra-(4-carboxylphenyl)ethylene (H4 TCPE) and Zn2+ . Complex 1 was formed by the close packing of Zn-TCPE hinge, and isostructural complexes 2-5 were constructed by the linkage of Zn-TCPE layer and pillar ligands. These complexes exhibit highly efficient multiphoton excited photoluminescence (MEPL) and concomitant third-harmonic generation (THG). The multiphoton absorption (MPA) parameters of 1 are superior to other multiphoton emission materials including the perovskite nanocrystals. The incorporation of pillar linkers slows down the charge transfer between layers of Zn-TCPE, and the aromatic core of pillar linkers has a great influence on the MPA performance of the corresponding frameworks.

Highly Efficient Multiphoton Absorption of Zinc‐AIEgen Metal–Organic Frameworks

AbstractA series of luminescent frameworks was synthesized from the selective combination of aggregation induced emission (AIE)‐linker tetra‐(4‐carboxylphenyl)ethylene (H4TCPE) and Zn2+. Complex 1 was formed by the close packing of Zn‐TCPE hinge, and isostructural complexes 2–5 were constructed by the linkage of Zn‐TCPE layer and pillar ligands. These complexes exhibit highly efficient multiphoton excited photoluminescence (MEPL) and concomitant third‐harmonic generation (THG). The multiphoton absorption (MPA) parameters of 1 are superior to other multiphoton emission materials including the perovskite nanocrystals. The incorporation of pillar linkers slows down the charge transfer between layers of Zn‐TCPE, and the aromatic core of pillar linkers has a great influence on the MPA performance of the corresponding frameworks.

Dielectric Properties of Fluorinated Aromatic Polyimide Films with Rigid Polymer Backbones.

Fluorinated aromatic polyimide (FAPI) films with rigid polymer backbones have been prepared by chemical imidization approach. The polyimide films exhibited excellent mechanical properties including elastic modulus of up to 8.4 GPa and tensile strength of up to 326.7 MPa, and outstanding thermal stability including glass transition temperature (Tg) of 346.3–351.6 °C and thermal decomposition temperature in air (Td5) of 544.1–612.3 °C, as well as high colorless transmittance of >81.2% at 500 nm. Moreover, the polyimide films showed stable dielectric constant and low dielectric loss at 10–60 GHz, attributed to the close packing of rigid polymer backbones that limited the deflection of the dipole in the electric field. Molecular dynamics simulation was also established to describe the relationship of molecular structure and dielectric loss.

Order–disorder structural tailoring and its effects on the chemical stability of (Gd, Nd)2(Zr, Ce)2O7 pyrochlore ceramic for nuclear waste forms

Series of unequal quantity Nd/Ce co-doped ceramic nuclear waste forms, (Gd, Nd)2(Zr, Ce)2O7, were prepared to tailor its ordered pyrochlore or disordered fluorite structure. The phase transition, microtopography, and elemental composition of the ceramic samples were systematically investigated, especially the effect of order-disorder structure on the chemical stability. It was confirmed that unequal quantity of Nd/Ce could synchronously replace the Gd/Zr-sites of Gd2Zr2O7. And the phase transition of order-disorder structure could be successfully tailored by regulating the average cationic radius ratio of (Gd, Nd)2(Zr, Ce)2O7 series. The elements of Gd, Nd, Zr, and Ce are uniformly distributed in the ordered or disordered structures. The MCC-1 leaching results showed that (Gd, Nd)2(Zr, Ce)2O7 pyrochlore ceramic nuclear waste forms had excellent chemical stability, whose elements' normalized leaching rates were as low as 10−4 -10−7 g‧m−2‧d−1 after 7 days. In particular, the chemical stability of disordered structure was superior to that of ordered structure. It was proposed that the force constant and the closest packing were changed with the structure transformation resulting the chemical stability difference.

A reentrant phase transition and a novel polymorph revealed in high-pressure investigations of CF4 up to 46.5 GPa.

The high-pressure behavior of simple molecular systems, devoid of strong intermolecular interactions, provides a unique avenue toward a fundamental understanding of matter. Tetrahalides of the carbon group elements (group 14), lacking all intermolecular interactions but van der Waals, are among the most elementary of molecular compounds. Here, we report the investigation of CF4 up to 46.5 GPa-the highest pressure up to which any tetrahalides of group 14 elements have been studied so far-by a combination of single-crystal x-ray diffraction (SC-XRDp), Raman spectroscopy, and ab initio calculations. These measurements reveal a pressure-induced reentrant phase transition (phase II →2.8GPa phase III →∼20GPa phase IIR) at room temperature and the formation of a previously unknown CF4 cubic polymorph, named phase IV, after the laser heating of CF4 at 46.5GPa. In this work, the structures of phases IIR, III, and IV were solved and the atomic coordinates were refined on the basis of SC-XRDp. A comparison of tetrahalides of group 14 elements underlines that reducing the intermolecular halogen-halogen distances leads to a structural rearrangement from close packing of the tetrahedral molecules to close packing of the halogen atoms.

Fluorous Metal–Organic Frameworks with Unique Cage-in-Cage Structures Featuring Fluorophilic Pore Surfaces for Efficient C 2 H 2 /CO 2 Separation

Fluorous Metal–Organic Frameworks with Unique Cage-in-Cage Structures Featuring Fluorophilic Pore Surfaces for Efficient C ₂ H ₂ /CO ₂ Separation

A case of antiferrochirality in a liquid crystal phase of counter-rotating staircases

Helical structures continue to inspire, prompted by examples such as DNA double-helix and alpha-helix in proteins. Most synthetic polymers also crystallize as helices, which relieves steric clashes by twisting, while keeping the molecules straight for their ordered packing. In columnar liquid crystals, which often display useful optoelectronic properties, overall helical chirality can be induced by inclusion of chiral chemical groups or dopants; these bias molecular twist to either left or right, analogous to a magnetic field aligning the spins in a paramagnet. In this work, however, we show that liquid-crystalline columns with long-range helical order can form by spontaneous self-assembly of straight- or bent-rod molecules without inclusion of any chiral moiety. A complex lattice with Fddd symmetry and 8 columns per unit cell (4 right-, 4 left-handed) characterizes this “antiferrochiral” structure. In selected compounds it allows close packing of their fluorescent groups reducing their bandgap and giving them promising light-emitting properties.

Explicit Analytical Solution for Random Close Packing in d=2 and d=3.

We present an analytical derivation of the volume fractions for random close packing (RCP) in both d=3 and d=2, based on the same methodology. Using suitably modified nearest neighbor statistics for hard spheres, we obtain ϕ_{RCP}=0.658 96 in d=3 and ϕ_{RCP}=0.886 48 in d=2. These values are well within the interval of values reported in the literature using different methods (experiments and numerical simulations) and protocols. This statistical derivation suggests some considerations related to the nature of RCP: (i)RCP corresponds to the onset of mechanical rigidity where the finite shear modulus emerges, (ii)the onset of mechanical rigidity marks the maximally random jammed state and dictates ϕ_{RCP} via the coordination number z, (iii)disordered packings with ϕ>ϕ_{RCP} are possible at the expense of creating some order, and z=12 at the fcc limit acts as a boundary condition.

Using good vibrations: Melting and controlled shear jamming of dense granular suspensions

Flows of suspensions can be blocked when the suspended particles are densely packed. This makes their formulation and their transport challenging in the industry. In this paper, we study the impact of vibrations on the behavior of dense granular suspensions prepared at a volume fraction above their jamming volume fraction but below the particle assembly random close packing. Vibrations are shown to have a strong effect on their rheological properties and to tune their transition from solidlike to liquidlike behavior. We study suspensions of rough silica particles in a Newtonian fluid. In the absence of vibrations, they have a solidlike behavior: they flow only above a yield stress. Particles are confined by the liquid interface, and the yield stress is of the frictional origin. When vibrations are applied, the yield stress vanishes to give rise to a liquidlike pseudo-Newtonian behavior at a low shear rate. Using shear-reversal experiments, we show that these liquidlike vibrated suspensions of frictional particles behave like nonvibrated suspensions of frictionless particles. As the shear rate is increased, we observe a shear thickening of the vibrated suspensions, eventually leading to shear-jamming. The yield stress behavior is recovered, and vibrations have no more impact. We show that this shear thickening can be tuned by changing the vibration energy injected into the system. We, finally, propose a physical picture based on the competition between contact opening by vibration and contact formation by shear to account for these behaviors. In the framework of the Wyart and Cates [Phys. Rev. Lett. 112, 098302 (2014)] model, vibrations can be seen as introducing a thermal-like repulsive force, yielding a critical stress proportional to the vibration stress introduced by Hanotin et al. [J. Rheol. 59, 253–273 (2015)].

Photoswitching of 5-phenylazopyrimidines in crystalline powders and thin films

Solid-state photoswitching enables the development of smart materials. However, the close packing of molecules and the lack of free volume in this state prevent sterically demanding structural changes induced by irradiation, thereby precluding the use of azobenzene photoswitches. Nevertheless, we report here the solid-state photoswitching of their derivatives, 5-phenylazopyrimidines, in crystalline powders and in amorphous thin layers. After identifying trans-cis photoisomerization by NMR spectroscopy, we demonstrated the applicability of 5-phenylazopyrimidines for future all-optical switching applications. For this purpose, we prepared thin films by spin-coating and confirmed their solid-state optical switching by optical transmission spectroscopy and their favorable surface topography by atomic force microscopy. Therefore, thin films of 5-phenylazopyrimidines are suitable for on-chip integration for emerging all-optical technologies.

A Combined Research Platform of Structural Morphology, Dealing with the Ordered 3D Space

The architecture of the human habitat and the whole domain of conceptual and physical space structures are mostly concerned with few basic 3D spatial features: 3D Space Networks- Lattices, Polyhedral (finite or infinite) close packing solids and space dividing surfaces. The inter- relation of these prime 3D features provides for the Quintuplet Phenomenology of 3D Space: 3D Networks are associated with close-packing arrays of polyhedra and every dual network pair is as- sociated with continuous surface partition, subdividing the space between the two. When combined with specific ‘symmetry regimes’, controlled by 3D Symmetry Space Groups, the focus is turned on Uniform 3D Space Networks-Lattices, with symmetrically identical vertex figures; on self-close- packing 3D polyhedra, and on highly symmetrical continuous surfaces, subdividing space between the dual, symmetrically identical 3D networks. Not even one of the a.m. features was exhaustively researched and enumerated in the past and that, mostly because no combined research platform was ever suggested. It is the author’s belief and conviction that such a platform might be generated and operated, when based on manipulative scanning of the fundamental domains that are associat- ed with the overall 3D Symmetry Space groups, provided that their exhaustive enumeration is com- plete.

Testing the adequacy of a simple theoretical model of dehydration optical clearing of collagen bundles: OCT measurements

Using optical coherence tomography, the scattering coefficients of collagen bundles are estimated at different levels of tissue hydration. We test the validity of a simple theoretical model of dehydration changes in the optical characteristics of a collagen bundle, which is considered as a system of parallel cylinders that model the collagen fibrils forming the bundle. The characteristics of scattering by individual scatterers are calculated using the Mie theory. To take into account the cooperative effects caused by the close packing of the scatterers, use is made of the standard packing function for a system of identical cylinders. The theoretical model also relies on a certain empirical law of changes in the hydration level of fibrils with a change in the water content in the tissue, which predetermines changes in the diameter and refractive index of fibrils during dehydration and rehydration of the tissue. It is shown that the theoretical estimates obtained using this model are in good agreement with the experimental data, which makes it possible to consider this model as reliable.

Axially chiral bay-tetraarylated perylene bisimide dyes as non-fullerene acceptors in organic solar cells

Chromophore shielding is critical for twisted single core perylene bisimides used as non-fullerene acceptors in organic solar cells. Inherent chirality becomes only important for close packing chromophores as single crystal structure analyses reveal.

Diameter-dependent single- and double-file stacking of squaraine dye molecules inside chirality-sorted single-wall carbon nanotubes.

The filling of single-wall carbon nanotubes (SWCNTs) with dye molecules has become a novel path to add new functionalities through the mutual interaction of confined dyes and host SWCNTs. In particular cases, the encapsulated dye molecules form strongly interacting molecular arrays and these result in severely altered optical properties of the dye molecules. Here, we present the encapsulation of a squaraine dye inside semiconducting chirality-sorted SWCNTs with diameters ranging from ∼1.15 nm, in which the dye molecules can only be encapsulated in a single-file molecular arrangement, up to ∼1.5 nm, in which two or three molecular files can fit side-by-side. Through the chirality-selective observation of energy transfer from the dye molecules to the surrounding SWCNTs, we find that the absorption wavelength of the dye follows a peculiar SWCNT diameter dependence, originating from the specific stacking of the dye inside the host SWCNTs. Corroborated by a theoretical model, we find that for each SWCNT diameter, the dye molecules adopt a close packing geometry, resulting in tunable optical properties of the hybrid when selecting a specific SWCNT chirality.

Revealing the characteristic length of random close packing via critical-like random pinning.

By randomly pinning particles in fluidized states and finding the local energy minima, we form static packings of mono-disperse disks that resemble random close packing, when only nc = 2.6% of the particles are pinned. The packings are isostatic and exhibit typical critical scalings of the jamming transition. The non-triviality of nc is manifested mainly in two aspects. First, nc acts as a critical point, leading to bifurcated critical scalings in its vicinity. The criticality of nc is also demonstrated in the packings of weakly polydisperse disks. Second, nc sets a length scale in agreement with the characteristic length of random close packing. With robust evidence, we show that this agreement is generally true for both mono- and poly-disperse particles and in both two and three dimensions. The randomness inherited from fluidized states by random pinning thus interprets the randomness of random close packing from a unique perspective.

Cluster structure of complex oxide melts

Structural cluster approach to non-crystalline condensed systems of oxide materials has been introduced as a result of many years’ experience of authors in the complex oxide melts research field. Nanoclusters distributed in a quasi-gas matrix form the structure of an oxide melt, possess the oxygen atoms’ close packing of regular polyhedrons where cations occupy its cavities. Nanoclusters and quasi-gas matrix are in the state of diffuse equilibrium at continuous interaction with each other.

Dense packings of geodesic hard ellipses on a sphere.

Packing problems are abundant in nature and have been researched thoroughly both experimentally and in numerical models. In particular, packings of anisotropic, elliptical particles often emerge in models of liquid crystals, colloids, and granular and jammed matter. While most theoretical studies on anisotropic particles have thus far dealt with packings in Euclidean geometry, there are many experimental systems where anisotropically-shaped particles are confined to a curved surface, such as Pickering emulsions stabilized by ellipsoidal particles or protein adsorbates on lipid vesicles. Here, we study random close packing configurations in a two-dimensional model of spherical geodesic ellipses. We focus on the interplay between finite-size effects and curvature that is most prominent at smaller system sizes. We demonstrate that on a spherical surface, monodisperse ellipse packings are inherently disordered, with a non-monotonic dependence of both their packing fraction and the mean contact number on the ellipse aspect ratio, as has also been observed in packings of ellipsoids in both 2D and 3D flat space. We also point out some fundamental differences with previous Euclidean studies and discuss the effects of curvature on our results. Importantly, we show that the underlying spherical surface introduces frustration and results in disordered packing configurations even in systems of monodispersed particles, in contrast to the 2D Euclidean case of ellipse packing. This demonstrates that closed curved surfaces can be effective at introducing disorder in a system and could facilitate the study of monodispersed random packings.

Electronic structure and magnetic coupling in selenium substituted pyridine-bridged bisdithiazolyl multifunctional molecular materials.

Bisdithiazolyl radicals have furnished in recent years multiple examples of molecular materials with promising conductive and magnetic properties. The electronic band structure and magnetic ordering in four different isostructural pyridine-bridged bisdithiazolyl and Selenium substituted compounds have been studied by means of hybrid DFT based methods as implemented in the CRYSTAL code. The full rationalization of the properties of these multifunctional magnetic molecular materials requires a careful description of their complex open-shell electronic structure. The results describe the systems as narrow band (0.2-0.3 eV dispersion) open-shell semiconductors with a gap of 1.15-1.40 eV between the valence and conducting bands. The bands defining the insulating gap are dominated by orbital contributions arising from the heteroatoms sitting in the outer rings. A low energy closed-shell metallic solution is found at 0.25-0.35 eV above the magnetic solutions thus suggesting a complex mechanism for electric conduction with band and hopping contributions. The observed trend of the conductivity is in line with the variation of the insulating gap but more rigorous modelling is required to take into account the details of the band structure of the systems. For all the systems the spin density is well localised on the molecular units and is independent of the magnetic solution. Thus the system can be described as an ensemble of well-defined S = 1/2 magnetic centres using a two-body Heisenberg-Dirac-van Vleck spin Hamiltonian. The lowest energy electronic solutions are in line with the observed magnetic behaviour at low temperature. The set of competing magnetic exchange interactions that emerges from using a suitable mapping to consistently describe the low energy magnetic solutions explains the variety of magnetic responses (absence of long-range magnetic order, antiferromagnetism or ferromagnetism) of the four studied compounds at low temperatures.

Characterization of the Stretch Flangeabitity of High-Strength Bainitic Steel: The Significance of Variant Pairs.

Variant pairs have an indispensable function on mechanical properties such as low impact toughness. Therefore, it was assumed that they would also affect the HER (Hole Expansion Ratio, an indicator to evaluate stretch flanging performance). To clarify this, a comprehensive analysis of the common influential factors in an 800 MPa grade low carbon micro-alloyed steel, i.e., the retained austenite, the M/A (Martensite/Austenite) island, the titanium precipitations, the grain diameter, the density of high angle grain boundaries and the textures, was first conducted. It was found that they did not match well with the HER, suggesting that they were not the governing factor for HER in this steel. However, the dominating crystallography groups and the variant pairing results indicated that they fitted well with the HER. In the samples with high HERs, the CP (Close Packed) groups dominated the transformation, wherein one individual CP group consisted of two or more Bain groups, whereas it evolved into the domination of joint CP groups and Bain groups for the low HER sample. Further analysis on the variant pairing features indicated that a correlation occurred between the HER and the high angle variant pairs. In the steels with high HERs, high-angle variant pairs of V1/V2, V1/V3 that transformed from the same CP group, particularly of V1/V2 pair, were mostly generated. They turned to V1/V9, V1/V10, V1/V12, V1/V15, V1/V17, and V1/V18 pairs from differential CP groups, especially the V1/V12 and V1/V15 pair for low-HER steel. This result showed that V1/V2, V1/V12, and V1/V15 might have accounted most for the HER in this steel. The underlying reason was that the V1/V2 pair was specialized in supplying a slip passage for dislocation transmission across a grain boundary with little resistance, whereas the dislocation transmission ability for V1/V12 and V1/V15 pair was particularly poor. Thus, to efficiently enhance the HER, one should regulate the variant pairs by augmenting the V1/V2 fraction and suppressing the formation of the V1/V12 and V1/V15 pair.

Enhanced Flame Retardancy in Ethylene–Vinyl Acetate Copolymer/Magnesium Hydroxide/Polycarbosilane Blends

A polymer ceramic precursor material—polycarbosilane (PCS)—was used as a synergistic additive with magnesium hydroxide (MH) in flame-retardant ethylene–vinyl acetate copolymer (EVA) composites via the melt-blending method. The flame-retardant properties of EVA/MH/PCS were evaluated by the limiting oxygen index (LOI) and a cone calorimeter (CONE). The results revealed a dramatic synergistic effect between PCS and MH, showing a 114% increase in the LOI value and a 46% decrease in the peak heat release rate (pHRR) with the addition of 2 wt.% PCS to the EVA/MH composite. Further study of the residual char by scanning electron microscopy (SEM) proved that a cohesive and compact char formed due to the ceramization of PCS and close packing of spherical magnesium oxide particles. Thermogravimetric analysis coupled with Fourier-transform infrared spectrometry (TG–FTIR) and pyrolysis–gas chromatography coupled with mass spectrometry (Py–GC/MS) were applied to investigate the flame-retardant mechanism of EVA/MH/PCS. The synergistic effect between PCS and MH exerted an impact on the thermal degradation products of EVA/MH/PCS, and acetic products were inhibited in the gas phase.