Odd-Even Alkyl Chain Effects on the Structure and Charge Carrier Transport of Two-Dimensional Sn-Based Perovskite Semiconductors.

Oscillations in the chemical or physical properties of materials, composed of an odd or even number of connected repeating methylene units, are a well-known phenomenon in organic chemistry and materials science. So far, such behavior has not been reported for the important class of materials, perovskite semiconductors. This work reports a distinct odd-even oscillation of the molecular structure and charge carrier transport properties of phenylalkylammonium two-dimensional (2D) Sn-based perovskites in which the alkyl chains in the phenylalkylammonium cations contain varying odd and even carbon numbers. Density functional theory calculations and grazing-incidence wide-angle X-ray scattering characterization reveal that perovskites with organic ligands containing an alkyl chain with an odd number of carbon atoms display a disordered crystal lattice and tilted inorganic octahedra accompanied by reduced mobilities. In contrast, perovskites with cations of an even number of carbon atoms in the alkyl chain form more ordered crystal structures, resulting in improved charge carrier mobilities. Our findings disclose the importance of minor changes in the molecular conformation of organic cations have an effect on morphology, photophysical properties, and charge carrier transport of 2D layered perovskites, showcasing alkyl chain engineering of organic cations to control key properties, of layered perovskite semiconductors.

Temperature dependence of the dynamics and interfacial width in nanoconfined polymers via atomistic simulations.

We present a detailed computational study on the temperature effect of the dynamics and the interfacial width of unentangled cis-1,4 polybutadiene linear chains confined between strongly attractive alumina layers via long, several µs, atomistic molecular dynamics simulations for a wide range of temperatures (143-473 K). We examine the spatial gradient of the translational segmental dynamics and of an effective local glass temperature (TgL). The latter is found to be much higher than the bulk Tg for the adsorbed layer. It gradually reduces to the bulk Tg at about 2 nm away from the substrate. For distant regions (more than ≈1.2nm), a bulk-like behavior is observed; relaxation times follow a typical Vogel-Fulcher-Tammann dependence for temperatures higher than Tg and an Arrhenius dependence for temperatures below the bulk Tg. On the contrary, the polymer chains at the vicinity of the substrate follow piecewise Arrhenius processes. For temperatures below about the adsorbed layer's TgL, the translational dynamics follows a bulk-like (same activation energy) Arrhenius process. At higher temperatures, there is a low activation energy Arrhenius process, caused by high interfacial friction forces. Finally, we compute the interfacial width, based on both structural and dynamical definitions, as a function of temperature. The absolute value of the interfacial width depends on the actual definition, but, regardless, the qualitative behavior is consistent. The interfacial width peaks around the bulk Tg and contracts for lower and higher temperatures. At bulk Tg, the estimated length of the interfacial width, computed via the various definitions, ranges between 1.0 and 2.7 nm.

Topology sorting: Separating linear/star polymer blend components by imbibition in nanopores.

We report the imbibition and adsorption kinetics of a series of symmetric linear/star cis-1,4-polyisoprene blends within the long channels of self-ordered nanoporous anodic aluminum oxide (abbreviated: AAO). Using in situ nanodielectric spectroscopy, we followed the evolution of the longest chain modes in the blends with a judicious selection of molar masses for the constituent components. We demonstrated differences in the imbibition kinetics of linear and star components based on the relative viscosities (e.g., polymers with lower zero-shear viscosity penetrated first the nanopores). Following the complete imbibition of the pores, the adsorption time, τads, of each component was evaluated from the reduction in the dielectric strength of the respective chain modes. In the majority of blends, both components exhibited slower adsorption kinetics with respect to the homopolymers. The only exception was the case of entangled stars mixed with shorter linear chains, the latter acting as a diluent for the star component. This gives rise to what is known as topology sorting, e.g., the separation of linear/star blend components in the absence of solvent. Moreover, a simple relation (τads ∼ 10 × tpeak; tpeak is the time needed for the complete filling of pores) was found for linear polymers and stars. This suggested that the characteristic timescale of imbibition (tpeak) governs the adsorption process of polymers. It further implied the possibility of predicting the adsorption times of high molar mass polymers of various architectures by the shorter imbibition times.

Capillary filling of star polymer melts in nanopores.

The topology of a polymer profoundly influences its behavior. However, its effect on imbibition dynamics remains poorly understood. In the present work, capillary filling (during imbibition and following full imbibition) of star polymer melts was investigated by molecular dynamics simulations with a coarse-grained model. The reversal of imbibition dynamics observed for linear-chain systems was also present for star polymers. Star polymers with short arms penetrate slower than the prediction of the Lucas-Washburn equation, while systems with long arms penetrate faster. The radius of gyration increases during confined flow, indicating the orientation and disentanglement of arms. In addition, the higher the functionality of the star polymer, the more entanglement points are retained. Besides, a stiff region near the core segments of the stars is observed, which increases in size with functionality. The proportion of different configurations of the arms (e.g., loops, trains, tails) changes dramatically with the arm length and degree of confinement but is only influenced by the functionality when the arms are short. Following full imbibition, the different decay rates of the self-correlation function of the core-to-end vector illustrate that arms take a longer time to reach the equilibrium state as the functionality, arm length, and degree of confinement increase, in agreement with recent experimental findings. Furthermore, the star topology induces a stronger effect of adsorption and friction, which becomes more pronounced with increasing functionality.

Nopadiene: A Pinene-Derived Cyclic Diene as a Styrene Substitute for Fully Biobased Thermoplastic Elastomers.

The bicyclic 1,2-substituted, 1,3-diene monomer nopadiene (1R,5S)-2-ethenyl-6,6-dimethylbicyclo[3.1.1]hept-2-ene was successfully polymerized by anionic and catalytic polymerization. Nopadiene is produced either through a facile one-step synthesis from myrtenal via Wittig-olefination or via a scalable two-step reaction from nopol (10-hydroxymethylene-2-pinene). Both terpenoids originate from the renewable ß-pinene. The living anionic polymerization of nopadiene in apolar and polar solvents at 25 °C using organolithium initiators resulted in homopolymers with well-controlled molar masses in the range of 5.6-103.4 kg·mol-1 (SEC, PS calibration) and low dispersities (D) between 1.06 and 1.18. By means of catalytic polymerization with Me4CpSi(Me)2NtBuTiCl2 and (Flu)(Pyr)CH2Lu(CH2TMS)2(THF), the 1,4 and 3,4- microstructures of nopadiene are accessible in excellent selectivity. In pronounced contrast to other 1,3-dienes, the rigid polymers of the sterically demanding nopadiene showed an elevated glass temperature, Tg,∞ = 160 °C (in the limit of very high molar mass, Mn). ABA triblock copolymers with a central polymyrcene block and myrcene content of 60-75 mol %, with molar masses of 100-200 kg/mol were prepared by living anionic polymerization of the pinene-derivable monomers nopadiene and myrcene. This diene copolymerization resulted in thermoplastic elastomers displaying nanophase separation at different molar ratios (DSC, SAXS) and an upper service temperature about 30 K higher than that for traditional petroleum-derived styrenic thermoplastic elastomers due to the high glass temperature of polynopadiene. The materials showed good thermal stability at elevated temperatures under nitrogen (TGA), promising tensile strength and ultimate elongation of up to 1600%.

A Terrylene-Anthraquinone Dyad as a Chromophore for Photothermal Therapy in the NIR-II Window.

A terrylenedicarboximide-anthraquinone dyad, FTQ, with absorption in the second near-infrared region (NIR-II) is obtained as a high-performance chromophore for photothermal therapy (PTT). The synthetic route proceeds by C-N coupling of amino-substituted terrylenedicarboximide (TMI) and 1,4-dichloroanthraquinone followed by alkaline-promoted dehydrocyclization. FTQ with extended π-conjugation exhibits an optical absorption band peaking at 1140 nm and extending into the 1500 nm range. Moreover, as determined by dielectric spectroscopy in dilute solutions, FTQ achieves an ultrastrong dipole moment of 14.4 ± 0.4 Debye due to intense intramolecular charge transfer. After encapsulation in a biodegradable polyethylene glycol (DSPE-mPEG2000), FTQ nanoparticles (NPs) deliver a high photothermal conversion efficiency of 49% under 1064 nm laser irradiation combined with excellent biocompatibility, photostability, and photoacoustic imaging capability. In vitro and in vivo studies reveal the great potential of FTQ NPs in photoacoustic-imaging-guided photothermal therapy for orthotopic liver cancer treatment in the NIR-II window.

Dynamically and structurally heterogeneous 1-propanol/water mixtures.

1-propanol/water mixtures over the whole composition range (0 < XV ≤ 1; XV is the 1-propanol volume fraction) are shown to be structurally and dynamically heterogeneous. By combining structural (x-ray diffraction), thermodynamic (differential scanning calorimetry) and dynamical probes (dielectric spectroscopy) we construct the pertinent phase diagram. It consists of liquid 1-propanol, liquid water, hexagonal ice and different hydrates, the latter sharing the same lattice. The phase diagram can be discussed in terms of four regimes, all having in common a droplet arrangement of the minority component. When water droplets are strongly confined by 1-propanol (regime I, 0.92 < XV ≤ 1; "soft" confinement), water is unable to crystallize. It has dynamics reminiscent to the ultra-viscous water phase known as high-density liquid (HDL). When water droplets are moderately confined (regime II, 0.75 < XV ≤ 0.92) water can crystallize via homogeneous nucleation. Strikingly, the homogeneous nucleation temperature is at 205 K, well within "no-man's land." The result is in line with earlier reports that soft confinement is the key to enter into the "no-man's land". When 1-propanol is the minority component (regimes III and IV), the structure and the dynamics are dominated by the 1-propanol/water interface with the formation of hydrates. The corresponding dynamical features suggest a link between hydrate formation and the two metastable phases of ultra-viscous water, HDL and low-density liquid.

Ordering kinetics of a tapered copolymer based on isoprene and styrene.

High molar mass copolymers with a tapered interface are mechanically tough materials with an accessible order-to-disorder transition temperature and hence processability. We report the first ordering kinetics for a tapered tetrablock copolymer in comparison to a conventional diblock copolymer made sequentially. We show that tapered copolymers belong to the Brazovskii "universality class," where fluctuations play a dominant role. Consequently, the order-to-disorder transition has a very weak, fluctuation-induced first-order character. The ordering kinetics of the lamellar phase from the supercooled disordered melt revealed several distinct differences associated with the range of metastability (increased), the timescales (bimodal), and the exact mechanism of ordering. The results are discussed in terms of the reduced interaction parameter and the introduction of structural defects within the lamellar grains.

Layers of Distinct Mobility in Densely Grafted Dendrimer Arborescent Polymer Hybrids.

Melts of multiarm stars of 1,4-polybutadiene (dendrimer arborescent hybrids) with very high branching functionality (f) and small arm molar mass behave as jammed colloids and show distinct layers of segmental mobility. Three mobility layers were identified, comprising outer, intermediate, and near-core segments, all displaying a Vogel-Fulcher-Tammann temperature dependence. The respective glass temperatures increase as f^{1/2}. Our findings pave the way for further progress in this field by reconsidering previous theoretical treatments based on a single friction coefficient in hybrid nanoparticles such as densely grafted stars.

Effect of confinement on the dynamics of 1-propanol and other monohydroxy alcohols.

We report the effect of confinement on the dynamics of three monohydroxy alcohols (1-propanol, 2-ethyl-1-hexanol, and 4-methyl-3-heptanol) differing in their chemical structure and, consequently, in the dielectric strength of the "Debye" process. Density functional theory calculations in bulk 1-propanol identified both linear and ring-like associations composed of up to five repeat units. The simulation results revealed that the ring structures, with a low dipole moment (∼2 D), are energetically preferred over the linear assemblies with a dipole moment of 2.18 D per repeat unit. Under confinement in nanoporous alumina (in templates with pore diameters ranging from 400 to 20 nm), all dynamic processes were found to speed up irrespective of the molecular architecture. The characteristic freezing temperatures of the α and the Debye-like processes followed the pore size dependence: Ta,D=Ta,D bulk-A/d1/2, where d is the pore diameter. The characteristic "freezing" temperatures for the Debye-like (the slow process for confined 1-propanol is non-Debye) and the α-processes decrease, respectively, by 6.5 and 13 K in confined 1-propanol, by 9.5 and 19 K in confined 2-ethyl-1-hexanol, and by 9 and 23 K in confined 4-methyl-3-heptanol within the same 25 nm pores. In 2-ethyl-1-hexanol, confinement reduced the number of linearly associated repeats from approximately heptamers in the bulk to dimers within 25 pores. In addition, the slower process in bulk 2-ethyl-1-hexanol and 4-methyl-3-heptanol, where the signal is dominated by ring-like supramolecular assemblies, is clearly non-Debye. The results suggest that the effect of confinement is dominant in the latter assemblies.

Interfacial Interactions During In Situ Polymer Imbibition in Nanopores.

Using in situ nanodielectric spectroscopy we demonstrate that the imbibition kinetics of cis-1,4-polyisoprene in native alumina nanopores proceeds in two time regimes both with higher effective viscosity than bulk. This finding is discussed by a microscopic picture that considers the competition from an increasing number of chains entering the pores and a decreasing number of fluctuating chain ends. The latter is a direct manifestation of increasing adsorption sites during flow. At the same time, the longest normal mode is somewhat longer than in bulk. This could reflect an increasing density of topological constraints of chains entering the pores with the longer loops formed by other chains.

H-Shaped Copolymer of Polyethylene and Poly(ethylene oxide) under Severe Confinement: Phase State and Dynamics.

The self-assembly and the dynamics of an H-shaped copolymer composed of a polyethylene midblock and four poly(ethylene oxide) arms (PE-b-4PEO) are investigated in the bulk and under severe confinement into nanometer-spaced LAPONITE clay particles by means of small- and wide-angle X-ray diffraction (SAXS, WAXS), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), rheology, and dielectric spectroscopy (DS). Because of the H-shaped architecture, the PE midblock is topologically frustrated and thus unable to crystallize. The superstructure formation in the bulk is dictated solely by the PEO arms as inferred by the crystallization/melting temperature relative to the PEO homopolymer. Confinement produced remarkable changes in the interlayer distance and PEO crystallinity but left the local segmental dynamics unaltered. To reconcile all structural, thermodynamic, and dynamic effects, a novel morphological picture is proposed with interest in emulsions. Key parameters that stabilize the final morphology are the severe chain confinement with the associated entropy loss and the presence of interactions (hydrophobic/hydrophilic) between the LAPONITE and the PEO/PE blocks.

Crystallization and Dynamics of Water Confined in Model Mesoporous Silica Particles: Two Ice Nuclei and Two Fractions of Water.

The crystallization and dynamics of water confined in model mesoporous silica particles (pore diameters ranging from 2.1 to 5 nm; pore length ≈ 1 µm) are studied in homogeneous aqueous suspensions by dielectric spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance (NMR) techniques. We establish the phase diagram ( T vs 1/ d) of confined water covering a broad range of pore diameters. A linear dependence of the heterogeneous and the homogeneous nucleation temperatures on the inverse pore diameter is shown. The two lines converge at a pore diameter of ∼2.6 nm, below which formation of stable crystals is suppressed. By combining dielectric spectroscopy and different NMR techniques, we determine the dynamics of water within mesoporous silica over broad temperature and frequency ranges. Both techniques identify two dynamically distinguishable fractions of confined water coexisting within the pores. We attribute the two fractions to an interfacial water layer at the pore walls and confined water in the pore interior. Two alternative scenarios are proposed to rationalize the coexistence of two dynamically distinguishable water fractions. In the first scenario, two liquid fractions of water coexist under extreme confinement conditions for a range of temperatures; we discuss similarities with the two ultraviscous liquids (high-density liquid and low-density liquid) put forward for supercooled bulk water. In the second scenario, a liquid and a solid phase coexist; we conjecture that highly distorted and unstable crystal nuclei exist under extreme confinement that exhibit reorientation dynamics with time scales intermediate to the surrounding confined liquid and to bulk ice.

Theory on Capillary Filling of Polymer Melts in Nanopores.

A unified theory for the imbibition dynamics of entangled polymer melting into nanopores is presented. Experiments demonstrate the validity of t1/2 dependence but contradict the predictions of the classical Lucas-Washburn equation because of the prefactor. A reversal in dynamics of capillary filling is reported with increasing polymer molecular weight. Polymer imbibition under nanometer confinement can be discussed by two mechanisms: one is the standard hydrodynamic flow, resulting in a parabolic flow profile. When the inner wall has a strong attraction to the polymer, a layer of immobile chains is created, resulting in an increase of the effective viscosity and to slower imbibition. The other is the reptation model proposed by Johner et al., leading to a plug flow profile and to the reduction in the effective viscosity (faster imbibition). The reversal in dynamics of polymer imbibition can be explained by the competition between these two mechanisms.

Complex dynamics of capillary imbibition of poly(ethylene oxide) melts in nanoporous alumina.

Capillary penetration of a series of entangled poly(ethylene oxide) melts within nanopores of self-ordered alumina follows an approximate t1/2 behavior according to the Lucas-Washburn equation; t is the time. However, the dependence on the capillary diameter deviates from the predicted proportionality to d1/2; d is the pore diameter. We observed a reversal in the dynamics of capillary rise with polymer molecular weight. Chains with 50 entanglements (Mw ≤ 100 kg/mol) or less show a slower capillary rise than theoretically predicted as opposed to chains with more entanglements (Mw ≥ 500 kg/mol) that display a faster capillary rise. Although a faster capillary rise has been predicted by theory and observed experimentally, it is the first time to our knowledge that a slower capillary rise is observed for an entangled polymer melt under conditions of strong confinement (with 2Rg/d = 1). These results are discussed in the light of theoretical predictions for the existence of a critical length scale that depends on the molecular weight and separates the microscopic (d < d*) from the macroscopic (d > d*) regime.

Influence of chain topology on polymer crystallization: poly(ethylene oxide) (PEO) rings vs. linear chains.

The absence of entanglements, the more compact structure and the faster diffusion in melts of cyclic poly(ethylene oxide) (PEO) chains have consequences on their crystallization behavior at the lamellar and spherulitic length scales. Rings with molecular weight below the entanglement molecular weight (M < Me), attain the equilibrium configuration composed from twice-folded chains with a lamellar periodicity that is half of the corresponding linear chains. Rings with M > Me undergo distinct step-like conformational changes to a crystalline lamellar with the equilibrium configuration. Rings melt from this configuration in the absence of crystal thickening in sharp contrast to linear chains. In general, rings more easily attain their extended equilibrium configuration due to strained segments and the absence of entanglements. In addition, rings have a higher equilibrium melting temperature. At the level of the spherulitic superstructure, growth rates are much faster for rings reflecting the faster diffusion and more compact structure. With respect to the segmental dynamics in their semi-crystalline state, ring PEOs with a steepness index of ∼34 form some of the "strongest" glasses.

Homogeneous nucleation of predominantly cubic ice confined in nanoporous alumina.

The nucleation mechanism of water can be precisely regulated by confinement within nanoporous alumina. We found a transition from heterogeneous nucleation of hexagonal ice (Ih) to homogeneous nucleation of predominantly cubic ice (Ic) with decreasing pore diameter. These results lead to a phase diagram of water under confinement. It contains a (stable) predominant Ic form, a form known to exist only in the upper atmosphere. Possible applications range from cryopreservation to construction materials like cement.

Hexasubstituted Benzenes with Ultrastrong Dipole Moments.

Hexasubstituted benzenes have been synthesized with the highest known dipole moments, as determined by dielectric spectroscopy and DFT methods. Based on the preparation of 4,5-diamino-3,6-dibromophthalonitrile, combined with a novel method to synthesize dihydrobenzimidazoles, these benzene derivatives have dipole moments in excess of 10 debye. Such dipole moments are desirable in ferroelectrics, nonlinear optics, and in organic photovoltaics. Structure determination was achieved through single-crystal X-ray crystallography, and the optical properties were determined by UV/Vis absorption and fluorescence spectroscopy.

Dynamic heterogeneity in fully miscible blends of polystyrene with oligostyrene.

Binary blends of polystyrene with oligostyrene are perfectly miscible (χ=0) yet dynamically heterogeneous. This is evidenced by independent probing of the dipole relaxation perpendicular to the backbone by dielectric spectroscopy and molecular dynamics. The self-concentration model with a single intramolecular length scale qualitatively describes the slower segmental dynamics. A quantitative comparison based on MD, however, requires a composition-dependent length scale. The pertinent dynamic length scale that best describes the slow segmental dynamics in miscible blends relates to both intra- and intermolecular contributions.

Conductivity of Ionic Liquids In the Bulk and during Infiltration in Nanopores.

The conductivity of ionic liquids (ILs) in nanopores is essential when considering their application as materials for energy. However, no consensus has been reached about the influence of confinement on the mobility of the ions. A series of ILs bearing the same cation, 1-butyl-3-methylimidazolium ([BMIM]+), and six different anions ([Cl]-, [Br]-, [I]-, [BF4]-, [PF6]-, and [TFSI]-) with radii from 0.168 to 0.326 nm were investigated with respect to their self-assembly, the thermodynamics, and the ionic conductivity in the bulk, during flow and under confinement in cylindrical nanopores with sizes in the range from 400 to 25 nm. In the bulk, the [BMIM]+[X]- exhibits weak ordering as a result of cation-anion correlations (charge alteration peak), and nanophase separation of polar/apolar groups. Liquid-to-glass temperatures were found to differ by ∼50 K, their viscosities by a factor of ∼270, and their conductivities by a factor of 24 (all at a temperature of 303 K). Electrostatic interactions were largely responsible for variations in the glass temperature, the viscosity, and the conductivity. Confined ILs behave differently from the bulk. The majority of ILs in the bulk were prone to crystallization during heating but were unable to crystallize in the smaller pores. Changes in dc-conductivity were used as markers of the phase state. This allowed the construction of the effective phase diagrams under confinement. The ILs penetrate the pores with an effective viscosity of the order of their viscosity in their bulk state. However, within the pores the dc-conductivity was reduced relative to bulk, indicating the immobilization of ions at the pore walls. Hydrophobization of the pore walls by hexamethyldisilazane could partially restore the conductivity. ILs are model systems where the phase state and ion mobility can be controlled by confinement.