Polymers with advanced structural and supramolecular features synthesized through topochemical polymerization

Polymers are an integral part of our daily life. Hence, there are constant efforts towards synthesizing novel polymers with unique properties. As the composition and packing of polymer chains influence polymer''s properties, sophisticated control over the molecular and supramolecular structure of the polymer helps tailor its properties as desired. However, such precise control via conventional solution-state synthesis is challenging. Topochemical polymerization (TP), a solvent- and catalyst-free reaction that occurs under the confinement of a crystal lattice, offers profound control over the molecular structure and supramolecular architecture of a polymer and usually results in ordered polymers. In particular, single-crystal-to-single-crystal (SCSC) TP is advantageous as we can correlate the structure and packing of polymer chains with their properties. By designing molecules appended with suitable reactive moieties and utilizing the principles of supramolecular chemistry to align them in a reactive orientation, the synthesis of higher-dimensional polymers and divergent topologies has been achieved via TP. Though there are a few reviews on TP in the literature, an exclusive review showcasing the topochemical synthesis of polymers with advanced structural features is not available. In this perspective, we present selected examples of the topochemical synthesis of organic polymers with sophisticated structures like ladders, tubular polymers, alternating copolymers, polymer blends, and other interesting topologies. We also detail some strategies adopted for obtaining distinct polymers from the same monomer. Finally, we highlight the main challenges and prospects for developing advanced polymers via TP and inspire future directions in this area.

This perspective showcases the potential of topochemical polymerization as an effective tool for synthesizing polymers with advanced molecular and supramolecular structures.     

16‐(4‐Cyanobenzylidene)‐3β‐pyrrolidinoandrost‐5‐en‐17β‐ol monohydrate

In the title compound, C₃₁H₄₀N₂O·H₂O, the outer two six‐membered rings are in chair conformations, while the central ring is in an 8β,9α‐half‐chair conformation. The five‐membered ring adopts a 13β‐envelope conformation and the cyano­benzyl­idene moiety has an E configuration with respect to the hydroxyl group at position 17. The steroid nuclei are linked by intermolecular O—H?O and O—H?N hydrogen bonds to form a molecular network. The molecular packing has an interesting feature, with the steroids aligned parallel to the b axis, forming a closed loop through hydrogen bonds linked via water mol­ecules.     

REACTIONS OF TELLURIUM TETRAHALIDES WITH GLYCOLS

Abstract

Tellurium tetrahalides undergo reaction with glycols to yield three different products: O,O'-dioxotrihalotellurates; bis(alkoxy)dihalotellurium (IV) compounds and hexahalotellurates. The course of the reaction appears to be determined primarily by the nature of the glycol. The structure of dichlorobis(cis- 2-hydroxycyclohexyloxy)tellurium(IV) has been determined crystallographically     

Effects of spatial coherence on near-field spectra

Expressions are derived for the spectrum of the field generated by a planar, homogeneous, secondary source of any spectral distribution and of any state of spatial coherence. It is shown that the state of coherence affects the contributions of the homogeneous as well as the evanescent waves of the emitted field. The near-field spectra are studied in detail. The analysis is illustrated by examples.     

Quantum chemical DFT study of 4-azatricyclo [5.2.2.02,6] undecane-3,5,8-trione

Fourier-transform-Raman and infrared spectrum of 4-azatricyclo [5.2.2.0^2,6] undecane-3,5,8-trione were recorded and analyzed. The vibrational wavenumbers were examined theoretically using the Gaussian03 set of quantum chemistry codes, and the normal modes were assigned by potential energy distribution (PED) calculations. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with reported values of similar structures which makes this compound an attractive object for future studies of nonlinear optics. Optimized geometrical parameters of the compound are in agreement with similar reported structures. The red shift of the NH stretching wavenumber in the infrared spectrum from the computational wavenumber indicates the weakening of NH bond.     

High pressure phase transitions in organic solids II: X-ray diffraction study ofp-dichlorobenzene at high pressures

X-ray diffraction experiments onp-dichlorobenzene at high pressures show a transition at ～ 0.3 GPa, to a new phase, the diffraction pattern of which cannot be indexed on the anticipated low temperature monoclinic crystal structure. We have instead found an orthorhombic cell, very closely related to the low temperature monoclinic cell, for this new phase. This structure, which also occurs inp-diiodobenzene at ambient conditions, has cell constantsa =14.02,b = 6.06,c = 7.41Å andZ = 4. The space group is Pbca. This new phase has a non-β herring-bone structure, in contrast with the initialα phase which has aβ-structure with ribbon-like arrangement of molecules, with Cl-Cl contacts of ～ 4A between adjacent molecules. This implies that with pressure the halogen-halogen interaction in this compound plays a less dominant role in crystal engineering.     

Structural, thermal and electrical properties of PVA-LiCF3SO3 polymer electrolyte

The development of polymeric systems with high ionic conductivity is one of the main objectives in Li rechargeable battery. In the present study, the different composition of PVA-LiCF₃SO₃ polymer electrolyte has been prepared by solution cast technique using DMSO as solvent. The FTIR study confirms the polymer-salt complex formation. The amorphous nature of the polymer has been confirmed by XRD analysis. DSC measurements show decrease in T_g with increasing salt concentration. The temperature dependent conductivity obeys Arrhenius relationship. The maximum conductivity has been observed in the order of 7 × 10^− 4 S cm^− 1 for 25 mol% of LiCF₃SO₃. The activation energy has been found to be 0.16 eV. The two peaks have been observed in the dielectric loss spectrum which shows two types of relaxation α and β.     

FT-IR, FT-Raman and SERS spectra of Vitamin C

FT-IR and FT-Raman spectra of Vitamin c have been recorded and analysed. SERS spectrum was recorded is silver colloid. The molecule is thought to adsorb with the lactone ring in a tilted side on orientation with respect to the silver surface.