Synthesis, Gelation Properties and Photopolymerization of Macrocyclic Diacetylenedicarboxamides Derived from L‐Glutamic Acid and trans‐1,4‐Cyclohexanediol

Abstract

Novel macrocyclic diacetylene compounds derived from L‐glutamic acid and trans‐1,4‐cyclohexanediol have been synthesized and their gelation ability, photopolymerizability and aggregation state have been studied. Most of the compounds with decyl groups gelatinize hexane, cyclohexane, cyclohexene and carbon tetrachloride. Some of the compounds also gelatinize toluene and 2‐propanol. An FTIR spectroscopy study indicated hydrogen‐bonding in the gel state. An X‐ray crystallographic analysis of one of the macrocyclic compounds with methyl groups demonstrated a tubular assembly based on the face‐to‐face packing of the macrocyclic rings as a result of intermolecular hydrogen‐bonding. Upon photoirradiation, most of the gels changed their hue from colourless to red or orange, which suggests photopolymerization of the diacetylene moieties.

Polymers with advanced structural and supramolecular features synthesized through topochemical polymerization

“…Cyclic monomers containing multiple diacetylene units (macrocyclic diacetylenes, MCDA) are established as excellent precursors for the topochemical synthesis of PDA-based organic tubular polymers that possess nanometre-sized interior cavities. 2 d ,27 Suitably functionalized MCDAs containing multiple DA units self-stack into a columnar assembly through non-covalent interactions, 28 sometimes aided by templates, 29 forming a supramolecular nanotube. The subsequent 1,4-addition polymerization of the DA units along the columns results in nanotubular polymers, bearing PDA side-walls.…”

Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

“…Generally diacetylene (DA) moieties in the macrocycles are photostable in solid state because of their high rigidity . Therefore, the fluidity of the gel state is anticipated to promote topochemical polymerization reaction of such macrocycles.…”

“…Generally diacetylene (DA) moieties in the macrocycles are photostable in solid state because of their high rigidity. [51] Therefore, the fluidity of the gel state is anticipated to promote topochemical polymerization reaction of such macrocycles. Morin's group have designed and synthesized the macrocycle, 12, containing diacetylene moieties both inside and outside the macrocycles (Figure 9a).…”

Synthesis, gelation and topochemical polymerization of meta-linked oligophenylenebutadiynylene derivatives

“…To overcome these drawbacks, a different approach by self-assembly of butadiyne-containing monomers in the gel state, in which the critical parameters for the 1,4-addition can also be obtained, was developed. [19][20][21][22][23][24][25][26][27][28][29][30][31] This method allows for the preparation of large quantities of PDA in a much faster process without the need for the "perfect" solvent system as needed for crystal formation. Thus, it is not surprising that the polymerization in the gel state is an increasingly popular avenue to prepare various types of PDAs.…”