Mechanoactivated amorphization and photopolymerization of styryldipyryliums.

Conventional topochemical photopolymerization reactions occur exclusively in precisely-engineered photoactive crystalline states, which often produces high-insoluble polymers. To mitigate this, here, we report the mechanoactivation of photostable styryldipyrylium-based monomers, which results in their amorphization-enabled solid-state photopolymerization and produces soluble and processable amorphous polymers. A combination of solid-state nuclear magnetic resonance, X-ray diffraction, and absorption/fluorescence spectroscopy reveals the crucial role of a mechanically-disordered monomer phase in yielding polymers via photo-induced [2 + 2] cycloaddition reaction. Hence, mechanoactivation and amorphization can expand the scope of topochemical polymerization conditions to open up opportunities for generating polymers that are otherwise difficult to synthesize and analyze.

Topochemical Syntheses of Polyarylopeptides Involving Large Molecular Motions: Frustrated Monomer Packing Leads to the Formation of Polymer Blends.

We report the topochemical syntheses of three polyarylopeptides, wherein triazolylphenyl group is integrated into the backbone of peptide chains. We synthesized three different monomers having azide and arylacetylene as end-groups from glycine, L-alanine and L-valine. We crystallized these monomers and the crystal structures of two of them were determined by single-crystal X-ray diffractometry. Due to the steric constraints, both of these monomers crystallized with two molecules, viz. conformers A and B, in the asymmetric unit. Consistently, in both cases, the A-conformers are antiparallelly π-stacked and B-conformers are parallelly slip-stacked, exploiting weak interactions. Though the arrangements of molecules in the pristine crystals were unsuitable for topochemical reaction, upon heating, they undergo large motion inside the crystal lattice to reach a transient reactive orientation and thereby the self-sorted conformer stacks react to give a blend of triazole-linked polyarylopeptides having two different linkages. Due to the large molecular motion inside crystals, the product phase loses its crystallinity.

Cascading Effect of Large Molecular Motion in Crystals: A Topotactic Polymorphic Transition Paves the Way to Topochemical Polymerization.

A topochemical polymerization governed by a topotactic polymorphic transition is reported. A monomer functionalized with azide and an internal alkyne crystallized as an unreactive polymorph with two molecules in the asymmetric unit. The molecules are aligned in a head-to-head fashion, thereby avoiding the azide-alkyne proximity for the topochemical azide-alkyne cycloaddition (TAAC) reaction. However, upon heating, one of the two conformers underwent a drastic 180° rotation, leading to a single-crystal-to-single-crystal (SCSC) polymorphic transition to a reactive form, wherein the molecules are head-to-tail arranged, ensuring azide-alkyne proximity. The new polymorph underwent TAAC reaction to form a trisubstituted 1,2,3-triazole-linked polymer. These results, showing unexpected topochemical reactivity of a crystal due to the intermediacy of an SCSC polymorphic transition from an unreactive form to a reactive form, highlight that predicting topochemical reactivity by relying on the static crystal structure can be misleading.

Tuning the Regioselectivity of Topochemical Polymerization through Cocrystallization of the Monomer with an Inert Isostere.

Regiochemistry of topochemical reactions depends on the crystal packing and biasing the regiochemistry necessitates precise crystal engineering. The pristine crystals of monomer 1 upon topochemical azide-alkyne cycloaddition (TAAC) reaction give a 1 : 1 blend of 1,4- and 1,5-triazole-linked polymers due to the presence of two self-sorted reactive conformers in the crystal. We designed a binary isomorphous cocrystal of monomer 1 and a structurally similar dummy molecule 2 to limit the number of reactive conformers of 1 to one and thus to get one type of polymer. Equimolar solution of 1 and 2 in chloroform-acetone mixture gave two 1 : 1 cocrystals Co-I and Co-II. The Co-II, a chloroform adduct, on heating undergoes desolvation and polymorphic transition to Co-I. Co-I is isomorphic to 1 and 2 and possess self-sorted arrays of 1 and 2. Heating Co-I results in the TAAC polymerization giving 1,4-triazolyl-linked polymer of 1 selectively, showing the power of crystal engineering in regiocontrol.

Topochemical Cycloaddition Reaction between an Azide and an Internal Alkyne.

Here we report the synthesis of a trisubstituted-1,2,3-triazole-linked polymer using a topochemical azide-alkyne cycloaddition (TAAC) reaction. A cyclitol-derived monomer having an azide and an internal alkyne group was designed. The four hydroxy groups present in this monomer dictate its crystal packing such that the monomer molecules are arranged head-to-tail, thereby placing the internal alkyne and the azide units of adjacent molecules proximally. Although the alignment of the reactive groups in the monomer crystal is not favourable for a topochemical reaction, a reactive orientation can be achieved by the rotation of the reactive groups. Upon heating the crystals, the monomer underwent topochemical polymerization to yield the trisubstituted-1,2,3-triazole-linked-polycyclitol. This study demonstrates a new synthetic strategy for cycloaddition reaction between non-polarized internal alkynes and azides to yield trisubstituted triazoles.

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.

Topochemical polymerizations for the solid-state synthesis of organic polymers.

Topochemical polymerizations are solid-state reactions driven by the alignment of monomers in the crystalline state. The molecular confinement in the monomer crystal lattice offers precise control over the tacticity, packing and crystallinity of the polymer formed in the topochemical reaction. As topochemical reactions occur under solvent- and catalyst-free conditions, giving products in high yield and selectivity/specificity that do not require tedious chromatographic purification, topochemical polymerizations are highly attractive over traditional solution-phase polymer synthesis. By this method, polymers having sophisticated structures and desired topologies can be availed. Often, such ordered packing confers attractive properties to the topochemically-synthesized polymers. Diverse categories of topochemical polymerizations are known, such as polymerizations via [2+2], [4+4], [4+2], and [3+2] cycloadditions, and polymerization of diynes, triynes, dienes, trienes, and quinodimethanes, each of which proceed under suitable stimuli like heat, light or pressure. Each class of these reactions requires a unique packing arrangement of the corresponding monomers for the smooth reaction and produces polymers with distinct properties. This review is penned with the intent of bringing all the types of topochemical polymerizations into a single platform and communicating the versatility of these lattice-controlled polymerizations. We present a brief history of the development of each category and comprehensively review the topochemical synthesis of fully-organic polymers reported in the last twenty years, particularly in crystals. We mainly focus on the various molecular designs and crystal engineering strategies adopted to align monomers in a suitable orientation for polymerization. Finally, we analyze the current challenges and future perspectives in this research field.

Organogel-Derived Covalent-Noncovalent Hybrid Polymers as Alkali Metal-Ion Scavengers for Partial Deionization of Water.

We show that crown ethers (CEs) 1-5 congeal both polar and nonpolar solvents via their self-assembly through weak noncovalent interactions (NCIs) such as CH···O and CH···π interactions. Diisopropylidene-mannitol (6) is a known gelator that self-assembles through stronger OH···O H bonding. These two gelators together also congeal nonpolar solvents via their individual self-assembly. Gelator 6 self-assembles swiftly to fibers, which act as templates and attract CE to their surface through H bonding and thereby facilitate their self-assembly through weak NCI. Polymerization of styrene gels made from CE and 6, followed by the washing off of the sacrificial gelator 6, yields robust porous polystyrene-crown ether hybrid matrices (PCH), having pore-exposed CEs. These PCHs not only were efficient in sequestering alkali metal ions from aqueous solutions but also can be recycled. This novel use of organogels for making solid sorbents for metal-ion scavenging might be of great interest.

CuBr/TBHP-mediated synthesis of N-acyl sulfonimidamides via the oxidative cross-coupling of sulfonimidamides and aldehydes.

N-Acyl sulfonimidamides were synthesized via a Cu-catalyzed double C-H/N-H activation protocol. The imino end of sulfonimidamides was acylated using aldehyde as the acylating agent and t-butyl hydrogen peroxide (TBHP) as the oxidant in acetonitrile (MeCN) at 82 °C. The mild reaction conditions afforded low-to-moderate yields of N-acyl sulfonimidamides with high structural diversity.