Two Structurally Different Polymers from a Single Monomer.

We designed and synthesized a malonamide-derived monomer, containing azide and alkyne units, for topochemical polymerization to yield nylon (n,3). This monomer on crystallization gave two concomitant polymorphs M1 and M2. Both the polymorphs show crystal packings that are suitable for topochemical azide-alkyne cycloaddition polymerization. On heating, polymorph M1 reacts regiospecifically to give 1,4-disubstituted-1,2,3-triazolyl-linked polymer, whereas polymorph M2 yields 1,5-disubstituted-1,2,3-triazolyl-linked polymer regiospecifically. In the case of polymorph M1, polymerization proceeds perpendicular to the hydrogen bonding direction, whereas in M2, the reaction occurs along the hydrogen bonding direction. This results in the two structurally different polymers having distinct topologies. These single-crystal-to-single-crystal polymerizations allowed us to study their structure at atomic resolution by single-crystal X-ray diffraction. This is the first report on the topochemical synthesis of two structurally isomeric polymers from a single monomer.

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.