Order-disorder phase transition in a chaotic system

For soft-mode turbulence, which is essentially the spatiotemporal chaos caused by the nonlinear interaction between convective modes and Goldstone modes in electroconvection of homeotropic nematics, a type of order-disorder phase transition was revealed, in which a new order parameter was introduced as pattern ordering. We calculated the spatial correlation function and the anisotropy of the convective patterns as a 2D XY system because the convective wave vector could freely rotate in the homeotropic system. We found the hidden order in the chaotic patterns observed beyond the Lifshitz frequency f(L), and a transition from a disordered to a hidden ordered state occurred at the f(L) with the increase of the frequency of the applied voltages.     

Kinetics of Si2H2 produced by the 193 nm photolysis of disilane

Si₂H₂ species were produced through the 193 nm excimer laser photolysis of Si₂H₆. Time‐resolved photoionization mass spectrometry was employed to study the reaction kinetics of Si₂H₂. The lower limit of self‐reaction of Si₂H₂ was estimated, k(Si₂H₂ + Si₂H₂) ≥ (1.7 ± 0.5) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, through analysis of the decay traces. This rate constant was independent of a total pressure on the entire pressure range (p_total = 1–7 Torr). No reaction of Si₂H₂ with H₂, CH₄, SiH₄, and Si₂H₆ was confirmed. The decay rates of Si₂H₂ reacting with O₂, NO, and HCl exhibit negative dependence on the total pressure. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 136–141, 2001     

Synthesis of poly(cyclodiborazane)s by allylboration polymerization of dicyano compounds with trimethallylborane

Allylboration polymerization of α, ω-dicyanoalkanes with trimethallylborane produced the corresponding poly(cyclodiborazane)s in high yields. This polymerization includes the allylboration reaction of cyano groups and the following dimerization of iminoborane species. The intermediate iminoborane species were detected by IR measurement. The poly(cyclodiborazane)s obtained were found to be more stable toward air than those prepared by allylboration polymerization using triallylborane.     

Lewis-Pairing-Induced Electrochemiluminescence Enhancement from Electron Donor-Acceptor Diads Decorated with Tris(pentafluorophenyl)borane as an Electrochemical Protector

This study reports an effective peripheral decoration of organic donor-acceptor diads with B(C₆F₅)₃ for stabilizing electrogenerated radical ions. By employing a common p-type organic semiconductor benzothienobenzothiophene (BTBT) as the donor, tetracoordinate boron complexes showed improved solution electrochemiluminescence (ECL) intensity, reaching a 156-fold increase compared to that of the parent diad. The unprecedented Lewis-pairing-induced ECL enhancement is attributed to the multiple roles of B(C₆F₅)₃: 1) redistributing frontier orbitals, 2) facilitating electrochemical excitation, and 3) restricting molecular motions. Furthermore, B(C₆F₅)₃ converted the molecular arrangement of BTBT from conventional 2D herringbones into 1D π-stacks. This robust, highly ordered columnar nanostructure allowed red-shifting of the crystalline film ECL with electrochemical doping through the electronic coupling pathways of BTBT. Our approach will facilitate the development of elaborate metal-free ECL systems.     

Synthesis of well-defined azido and amino end-functionalized polystyrene by atom transfer radical polymerization

Mono and difunctional polystyrenes containing active halogenated end groups were prepared by atom transfer radical polymerization (ATRP). Substitution reactions were explored to convert the halogen termini to azido groups, followed by readuction to form the amino functional polymer. Quantitative conversion of the end groups was observed in each transformation reaction. ¹H NMR demonstrated the formation of the azide from the bromide functionality without elimination. The difunctional α,ω-diaminopolystyrene was reacted with terephthaloyl chloride in a condensation process to produce chain-extended polystyrene containing amide bonds along the polymer backbone.     

Irreversible Structural Phase Transition in [(9-triptycylammonium) ([18]crown-6)][Ni(dmit)2]: Origin and Effects on Electrical and Magnetic Properties

Materials exhibiting irreversible phase transitions, leading to changes in their properties, have a potential for novel application in electronic components such as a non-rewritable high-security memory. Here, we focused on the two salts, [(9-triptycylammonium)([18]crown-6)][Ni(dmit)₂] ( 1 ) and [(9-triptycylammonium)([15]crown-5)][Ni(dmit)₂] ( 2 ), which featured 2D sheet structures with alternately stacked cation and anion layers. Both salts exhibit similar cation arrangements, however, their anion arrangements differ significantly. The temperature-dependent magnetic susceptibilities of 1 and 2 were well reproduced by the alternating chain model (J_AC1/k_B=−306(8), J_AC2/k_B=−239(3) K) and the Curie-Weiss model (θ=−3.9(1) K), respectively. 1 experience a reversible phase transition around 40–60 K, causing anomalies in magnetic behavior. Moreover, an irreversible single-crystal-to-single-crystal phase transition to 1′ undergo at ~381 K, inducing a rearrangement of [Ni(dmit)₂]⁻ anions and a resistivity decrease from 6.5×10⁶ to 6.5×10² Ω cm. The susceptibility curve of 1′ was reproduced by a combination of the Curie-Weiss and dimer models (J_dimer/k_B=−407(5), θ=−26.7(5) K). The irreversible transition of 1 is the first example for such supramolecule and [Ni(dmit)₂]⁻ system to our knowledge, in opening potential new-type materials.     

Inside Back Cover: Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals (Angew. Chem. Int. Ed. 35/2023)

A one-stone, two-bird method to integrate the soft porosity and electrical properties of distinct metal–organic frameworks (MOFs) into a single material involves the design of conductive-on-insulating MOF (cMOF-on-iMOF) heterostructures that allow for direct electrical control. Herein, we report the synthesis of cMOF-on-iMOF heterostructures using a seeded layer-by-layer method, in which the sorptive iMOF core is combined with chemiresistive cMOF shells. The resulting cMOF-on-iMOF heterostructures exhibit enhanced selective sorption of CO₂ compared to the pristine iMOF (298 K, 1 bar, S from 15.4 of ZIF-7 to 43.2–152.8). This enhancement is attributed to the porous interface formed by the hybridization of both frameworks at the molecular level. Furthermore, owing to the flexible structure of the iMOF core, the cMOF-on-iMOF heterostructures with semiconductive soft porous interfaces demonstrated high flexibility in sensing and electrical “shape memory” toward acetone and CO₂. This behavior was observed through the guest-induced structural changes of the iMOF core, as revealed by the operando synchrotron grazing incidence wide-angle X-ray scattering measurements.