Intercalation of alkylamines into an organic polymer crystal

Abstract

Organic solid-state synthesis allows formation of products that are difficult or impossible to produce by conventional methods. This feature, and the high degree of reaction selectivity that can be achieved, is a direct result of the control over the relative orientation of the reactants afforded by the solid state. But as the successful development of 'topochemical reactions' requires the careful design of suitable reactant crystals, the range of both reactions and products amenable to this approach has been limited. However, recent advances in organic crystal engineering, particularly the rational design of complex solid architectures through supramolecular preorganization, have renewed interest in topochemical reactions. Previously, we have orientated muconate monomers--diene moieties with a carboxylate group on each end--using long-chain n-alkylammonium ions, such that the topochemical photopolymerization of the solid-state reactants produces layered crystals of stereoregular and high-molecular-mass polymers. Here we show that these polymer crystals are capable of repeated, reversible intercalation by conversion to the analogous poly(carboxylic acid), followed by transformation into a number of poly(alkylammonium muconate)s upon addition of the appropriate amine. Introduction of functional groups into these crystals may allow the design of organic solids for applications such as molecular recognition, separation and catalysis, thereby extending the range and practical utility of current intercalation compounds.

Self-Assembled Nanoreactors

“…293 Recent advances in organic crystal engineering, particularly the rational design of complex solid architectures through supramolecular preorganization, have renewed interest in topochemical reactions. [294][295][296][297][298][299] Although not many catalysis experiments have been carried out with these organic crystals, it is worth mentioning the possibility in this review. Organic analogues to zeolites and mesoporous sieves were developed by Miller et al 300 They made catalytically active, nanoporous organic materials based on cross-linked lyotropic liquid crystals and demonstrated their use as efficient catalysts in Knoevenagel condensations.…”

Polymer Structure Control Based on Crystal Engineering for Materials Design

“…Layered polymer crystals obtained by the topochemical polymerization of alkylammonium muconates and sorbates function as an intercalation compound [149][150][151] ( Figure 14). For example, the ammonium muconate polymer crystals are converted into poly(muconic acid) (PMA) crystals by hydrolysis with HCl in an aqueous methanol or by thermolysis in the solid state, and the process is reversible.…”

Organic Intercalation of Unsaturated Amines into Layered Polymer Crystals and Solid-State Photoreactivity of the Guest Molecules in Constrained Interlayers

“…This is in good agreement with the fact that short-chain alkylammonium (Z, Z)-muconates (m < 9) isomerize to the corresponding isomers under photoirradiation in the crystalline state, while long-chain alkylammonium (Z, Z)-muconates (10 > m) polymerize topochemically under similar conditions in our previous results. 21,28 Differing from the isomerization of M-1, the oleylammonium monomer M-2 topochemically polymerized to give an insoluble product under UV-irradiation in the crystalline state as expected. Figure 4 shows the IR spectra of the poly(oleylammonium muconate)s obtained by the intercalation and the polymerization.…”

“…21 The resulting polymer was isolated by removing the unreacted monomer with methanol. The hydrolysis of poly(dodecylammonium muconate) was carried out in HCl methanol solution (1 mol L −1 ) with stirring at room temperature for 1 h. IR spectroscopy confirmed the quantitative transformation.…”

“…[12][13][14][15] In contrast to a large number of studies on intercalation systems made of inorganic compounds or inorganic-organic hybrids, very few examples are known as an intercalation system consisting of organic compounds as both the host and guest. [16][17][18][19][20][21] We have previously demonstrated the fundamental features and mechanism of the intercalation of various alkylamines into poly(muconic acid) (PMA) as the organic host compound [21][22][23][24] (Scheme 1). Long-chain alkylamines are suitable as the guest molecules and the intercalation provides a new layered polymer crystal with an interlayer spacing different from that of the original PMA crystals.…”