MEASUREMENTS OF CHAIN INTERPENETRATION OF POLYMER GLASSES

The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale （several to tens of nanometer）. In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level.     

Structural tuning of coordination polymers by 4-connecting metal node and secondary building process

Due to variation in ligand's conformation, metal node's connecting geometry, and secondary building process by anions, bat-like, dumbell-like, diamondoid, or pillar-layer topologies are achieved.     

Two Zinc(II) Coordination Polymers Based on the Ligand 1, 4‐Bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene: Syntheses,Crystal Structures and Properties

Two coordination polymers (CPs), {[Zn₂(BMB)(5‐AIPA)₂] · 2H₂O}_n( 1 ) and [Zn(BMB)(5‐NIPA)]_n( 2 ) {BMB = 1, 4‐bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene, 5‐AIPA = 5‐aminoisophthalic acid, 5‐NIPA = 5‐nitroisophthalic acid}, were synthesized under hydrothermal conditions. Compound 1 displays a 2D double‐layer structure, which is packed into a 3D supramolecule by interlayer hydrogen bonds and π–π stacking interactions. Compound 2 displays a threefold interpenetrating 3D network, which is composed of left‐handed helical chains and two types of meso‐helical chains along different directions.     

Synthesis, structures and luminescent properties of Co(II) and Ni(II) metal-organic frameworks with semirigid diphthalic ligands

A series of transition metal coordination polymers [Co(H₃L)₂(4,4′- bpy)(H₂O)₂]_n?n(4,4′-bpy) (1), [Ni(H₂L)(4,4′-bpy)(H₂O)₂]_n (2), [Co₂(L)(phen)₂(H₂O)₄]_n?(H₂O)_2n (3), and [Ni₂(L)(phen)₂(H₂O)₄]_n?(H₂O)_2n (4) have been assembled from a semirigid multicarboxylate ligand 3,3′-(1,4-phenylenebis(oxy))diphthalic acid (H₄L) with the help of 4,4′-bipyridine (4,4′-bpy) ligand or 1,10-phenanthroline (phen) ligand. X-ray single crystal diffraction analysis reveals that complex 1 crystallizes in the space group of P − 1 and displays a one-dimensional (1D) chain structure constructed from 4,4′-bpy ligand and H₃L ligand, which was further interlinked to form a three-dimensional network via hydrogen bonds. In complex 2, Ni(II) atoms are coordinated by L ligand in monodentate fashion to form alternate left- and right-helices, which are further bridged together by the coordination interactions between Ni(II) atoms and 4,4′-bpy, leading to a 2-fold (4, 4)-connected interpenetrating network. Isostructural complexes 3 and 4 belong to the space group P − 1 and display a 1D chain structure constructed from phen and L ligands, which was further interlinked to form a 2D plane via π–π interactions. In addition, their thermal and luminescent properties were also investigated.     

Sol-gel preparation and properties of interpenetrating, encapsulating and blend silica-based urea-formaldehyde hybrid composite materials

Four different silica-based urea-formaldehyde (UF/SiO₂) composite materials were prepared by various sol-gel synthetic procedures to yield an interpenetrating (IPN-UF/SiO₂), a micro-size UF resin encapsulated inside silica shell (Encap-UF/SiO₂), a micro-size silica encapsulated inside UF shell (Encap-SiO₂/UF), and a blend mixture (Blend-UF/SiO₂) hybrid systems. The thermal properties of the obtained organic-inorganic hybrid composite materials were examined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The structure and morphology of the obtained systems were investigated by infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. Their surface porosity and acidity were evaluated from the nitrogen adsorption isotherm and the pH of the corresponding 10% aqueous suspension, respectively. All the results provided evidence for the formation of different hybrid systems with different surface, structural and morphological characteristics.     

Glorious uncertainty—challenges for network design

This article discusses the challenges that face the crystal engineer in the deliberate design of new network structures. These include control over ligand and metal coordination geometry, selection of network topology from a number of possibilities which all have the same connectivity, and control of methods of increasing packing efficiency, including interpenetration (both number of nets (including only one) and topology of interpenetration). These variables can lead to polymorphism and related phenomena, the bane of crystal engineers. Templation by counterions, guest molecules and/or solvents can also lead to unpredictable results.     

2D parallel interpenetration of [M2(bpp)4X4] [M, Fe(II)/Co(II); bpp, 4,4′-trimethylenedipyridine; X, SCN, SeCN and N3] complexes: Pseudohalide-dependent conformation of bpp

Three coordination complexes of Co(II)/Fe(II) with 4,4′-trimethylenedipyridine (bpp) and pseudohalides (SCN⁻, SeCN⁻ and N₃⁻) have been synthesized. The complexes have been characterized by X-ray single crystal structure determination. They are isomorphous having 2D layers in which two independent wavy nets display parallel interwoven structures. Pseudohalide binds metal centers through N terminal and occupies the trans axial positions of the octahedral metal coordination environment. Pseudohalide remains pendant on both sides of the polymeric layer and help the stacking through hydrogen bonding. The conformation of bpp in the interpenetrated nets is observed to be dependent on the choice of pseudohalide.     

Synthesizing Interpenetrated Triazine-based Covalent Organic Frameworks from CO2

Crystalline triazine-based covalent organic frameworks (COFs) are aromatic nitrogen-rich porous materials. COFs typically show high thermal/chemical stability, and are promising for energy applications, but often require harsh synthesis conditions and suffer from low crystallinity. In this work, we propose an environmentally friendly route for the synthesis of crystalline COFs from CO₂ molecules as a precursor. The mass ratio of CO₂ conversion into COFs formula unit reaches 46.3 %. The synthesis consists of two steps; preparation of 1,4-piperazinedicarboxaldehyde from CO₂ and piperazine, and condensation of the dicarboxaldehyde and melamine to construct the framework. The CO₂-derived COF has a 3-fold interpenetrated structure of 2D layers determined by powder X-ray diffraction, high-resolution transmission electron microscopy, and select-area electron diffraction. The structure shows a high Brunauer–Emmett–Teller surface area of 945 m² g⁻¹ and high stability against strong acid (6 M HCl), base (6 M NaOH), and boiling water over 24 hours. Post-modification of the framework with oxone has been demonstrated to modulate hydrophilicity, and it exhibits proton conductivity of 2.5×10⁻² S cm⁻¹ at 85 °C, 95 % of relative humidity.     

Different aliphatic dicarboxylates affected assemble of new coordination polymers constructed from flexible-rigid mixed ligands

In this article, seven coordination polymers: [Cd(C₅H₆O₄)(C₁₀H₈N₂)]_n (1), [Zn(C₅H₆O₄)(C₁₀H₈N₂)]_n (2), [Cd(C₆H₈O₄)(C₁₀H₈N₂)]_n (3), {[Mn(C₁₀H₈N₂)(H₂O)₄] (C₄H₄O₄)·4H₂O}_n (4), [Mn₅(C₄H₄O₄)₄(O)]_n (5), [Cd(C₄H₄O₄)(C₁₀H₈N₂)(H₂O)]_n (6) and [Zn(C₆H₆O₄)(C₁₂H₈N₂)(H₂O)]_n (7) were synthesized and characterized by single-crystallographic X-ray diffraction. Compounds 1 and 2 are two-dimensional layers connected by glutarate anions and 4,4′-bpy. Unlike compounds 1 and 2, compound 3 is a two-fold interpenetration network. Compound 4 is a one-dimensional chain-like structure, which is further extended to two-dimensional supramolecular layer structure with hydrogen bond. During the synthesis of compound 4, to our surprise, we got compound 5; compound 5 is an interesting three-dimensional network composed of pentanuclear Mn(II) building units and succinate anions. Compound 6 is also a two-dimensional supramolecular layer structure composed of one-dimensional chain-like structure with hydrogen bonds and Π-Π interactions. Compound 7 is also a one-dimensional chain-like structure, which is further connected with the same kind of interaction to generate two-dimensional supramolecular layer structure. Furthermore, compounds 1 and 2 both exhibit fluorescent property at room temperature.