Weak Interactions Dominating the Supramolecular Self-Assembly in a Salt: A Designed Single-Crystal-to-Single-Crystal Topochemical Polymerization of a Terminal Aryldiacetylene

Abstract

Single-crystal-to-single-crystal (SCSC) topochemical polymerizations of diacetylenes can yield nearly defect-free conjugated polymer crystals unattainable by other methods. Aryl-substituted diacetylenes with their potentially greater conjugation have been targeted for years, but until now no one has reported a SCSC polymerization of any aryl-substituted diacetylene. This is presumably due to the rigidity of such diaryl-substituted monomers as well as the lack of control over the supramolecular structure. To address this problem, the polymerization of a terminal phenyldiacetylene was targeted. It was assumed that a terminal diacetylene should demonstrate greater flexibility in the solid state. To establish the necessary (approximately 4.9 A) repeat distance, commensurate with the repeat distance in the polymer, a host-guest system was designed. The chosen diacetylene guest, the amine DABzNH(2), was to be crystallized with the oxalamide dicarboxylic acid host, H(2)og. The plan required a segregation of the hydrogen bonds, amide-amide hydrogen bonds to establish the 4.9 A spacing, and the carboxylate to ammonium ion hydrogen bonds to organize the guest. Prior to carrying out the diacetylene synthesis a series of model salts were studied. Consistent with the hydrophobic effect it was found that amines with large "greasy" substituents assembled according to the design. Once the model studies established that weak interactions could dominate the supramolecular structure of a salt, the actual design was put to the test. The targeted guest, DABzNH(2), was synthesized and crystals of the host-guest salt (DABzNH(3))(2)og were prepared. The resulting crystal structure was in complete accordance with the design. A SCSC polymerization was achieved by a slow annealing treatment lasting about three months. The crystal structure of the resulting polymer not only confirmed the first example of a poly(aryldiacetylene) single crystal, it also revealed an unexpected reaction pathway that shows a major movement involving the rigid aromatic substituent.

Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

“…The diyne systems are parallel as requested; nevertheless, the angle of the reactive carbons and mostly their distance separations are not favorable, being distorted and much too long, respectively (Figure 4). Topochemical polymerization of diacetylene is also prevented because there is no long range parallel stacking of diynes [58][59][60][61][62][63][64][65][66][67]. …”

Constructing π-Electron-Conjugated Diarylbutadiyne-Based Polydiacetylene under Molecular Framework Controlled by Hydrogen Bond and Side-Chain Substituent Position

“…By simply designing the butadiyne monomer with aryl groups instead of flexible chains at both ends, PDAs from diarylbutadiyne can be easily obtained. Based on this concept, some research has been reported . However, according to Baughman, the diarylbutadiyne molecule is rather photostable, which leads to the limitation of photopolymerization.…”

One-Pot Synthesis, Crystal Structures and Thermal Properties of Two Three-Dimensional Cobalt(II) Complexes

“…[1][2][3][4][5][6][7][8][9] It is widely acknowledged that the coordinative bonding is the primary interaction to sustain the network, while supramolecular interactions, such as hydrogen bonding, π-π stacking interactions and Van der Waals forces are also believed to play important roles. [10][11][12][13][14][15][16][17] To date, a variety of supramolecular polymers with complicated architectures and interesting properties based on different bridging ligands especially aromatic polycarboxylate ligands have been synthesized successfully.…”