No abstract

Crystalline coordination polymers of organic polymers (CPOPs) were synthesized via photopolymerization of Ag(I) coordination polymers of dienes which have a self-templating nature due to the formation of N-H···O hydrogen bonded layers. The shock absorbing nature of the H-bonded layer facilitated the SCSC [2+2] transformation upon irradiation to produce CPOPs.

The quest for synthetic polymers is ever growing field given their potential uses in various day-today applications. The need for the fabrication of novel polymers demands new strategies in chemistry and material science for alternative raw materials which enable a controlled arrangement of monomers for polymerization reaction to lead to useful materials. A novel organic polymer containing cyclobutanes and amides as back bones and pyridyl groups as side arms has been synthesized by single-crystal-to-single-crystal (SCSC) [2+2] photopolymerization reaction in the coordination polymers (CPs) of diene. The diene molecule is photo inactive in its crystals and forms a triply intertwined one-dimensional helical CPs with Cd(NO3)2 and Cu(NO3)2 salts. The 1D-CPs is transformed in to coordination polymer of organic polymer (CPOPs) containing 3-fold interpenetrated 3D-networks of CdSO4 topology via [2+2] reaction in SCSC manner upon irradiation. The organic polymer was isolated from CPOPs and characterized by 1H NMR, 13C NMR, MALDI-TOF, GPC and XRPD. Further, it was found that the organic polymer is amenable for N-alkylation reactions such as methylation, propylation and decylation. The formate salt of organic polymer and methylated polymer were shown to form plastic films with combination of properties such as high transparency, tensile strengths, gas permeability, thermal stabilities, resistance for water and other organic solvents. The methylated polymer exhibited an ability to capture chromate ions and anionic dyes from aqueous solutions.

Electro-ionic soft actuators, capable of continuous deformations replacing noncompliant rigid mechanical components, attract increasing interest in the field of next-generation metaverse interfaces and soft robotics. Here, a novel MXene (Ti 3 C 2 T x ) electrode anchoring manganese-based 1,3,5-benzenetricarboxylate metal-organic framework (MnBTC) for ultrastable electro-ionic artificial muscles is reported. By a facile supramolecular self-assembly, the Ti 3 C 2 T x -MnBTC hybrid nanoarchitecture forms coordinate bond, hydrogen bond, and hydrophilic interaction with the conducting polymer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), resulting in a mechanically flexible and electro-ionically active electrode. The superior electrical and electrochemical performances of the electrode stem from the synergistic effects between intrinsically hierarchical nanoarchitecture of MnBTC and rapid electron transport behavior of Mxene, leading to fast diffusion and accommodation of ions in the ion-exchangeable membrane. The developed artificial muscle based on Ti 3 C 2 T x -MnBTC is found to exhibit high bending displacement (12.5 mm) and ultrafast response time (0.77 s) under a low driving voltage (0.5 V), along with wide frequency response (0.1-10 Hz) and exceptional stability (98% retention at 43,200 s) without any distortion of actuation performance. Furthermore, the designed electro-active artificial muscle is successfully used to demonstrate mimicry of eye motions including eyelid blinking and eyeball movement in a doll.

Getting selectively organized: Molecules of bis‐pyridyl dienes have been stereoselectively photodimerized to form their strained double [2+2] reaction products by using argentophilic forces (see scheme). A pronounced influence of anions and the efficiency of a mechanochemical synthesis have also been described.

The molecular isomers of a diene-containing amide and pyridine moieties revealed that they exhibit different crystal structures and reactivities. One of the isomer forms a two-fold interpenetrated diamonded network via N–H···N hydrogen bonds and undergoes a [2 + 2] photopolymerization in the solid-state despite having unfavorable criss-cross aligned double bonds.

The unsymmetrical bispyridyl olefins containing amides (UBOs) have been synthesized to study solid state [2 + 2] photochemical reactions with or without template. The crystal structures of UBOs were determined using a powder Xray diffraction technique. The pure organic materials of UBOs were found to form head-to-head (HH)-dimers upon irradiation in accordance with their crystal structures. Further, Ag•••Ag and Ag•••π interactions were shown to template headto-tail (HT) photodimerization of UBOs in their onedimensional-coordination polymers in single-crystal-to-singlecrystal manner. The dimer structures were determined by single crystal X-ray and 1 H NMR techniques.

Making metal−organic frameworks (MOFs) that are stabilized in nonpolar media is not as straightforward as making their inorganic nanoparticle counterparts, since surfactants penetrate through the porous structures or dissolve the secondary building units (SBUs) through ligand-exchange linker modulator mechanisms. Herein, we report that calixarenes stabilize UIO-66 nanoparticles effectively by remaining outside the grains through size exclusion, without pores becoming blocked, all the while providing amphiphilicity that permits the formation of stable colloidal dispersions with much narrower size distributions. Using the UIO-66 dispersed solutions, we show that smooth films from an otherwise immiscible polystyrene can be made feasibly.