A Novel, Soluble Poly(diacetylene) Containing an Aromatic Substituent

Abstract

A series of diacetylenic monomers containing at least one aromatic substituent were synthesized.Since the aromatic side group is a rigid, pyrimidyl ring, it is necessary that the other side group has a high degree of flexibility to permit polymerization in the monomer single crystal. Among the five monomers synthesized, only 8-[ [(butoxycarbonyl)methyl] urethanyl] -1-(5-pyrimidyl)octa-1,3-diyne (BPOD) monomer crystals turned into a polymer upon 7-irradiation with 68% monomer-to-polymer conversion. Poly(BPOD) is metallic red as polymerized and highly soluble in chloroform and undergoes a dramatic color transition from red Umax = 510 nm) to purple (Xm" = 599 nm) upon the addition of a nonsolvent such as hexane. This red-to-purple transition going from good to poor solvent is interpreted as a single-chain phenomenon. Aggregation may follow as the rigid chains interact with each other and crystallize. This aggregation could be prevented by increasing the side group-nonsolvent interaction by employing a nonsolvent which has high polarity and hydrogen-bonding capability.

Important role of Si main chain for solvatochromism in poly[bis(4‐propoxybutyl)silylene]

“…In recent years, the solvatochromism for a variety of polymers observed from absorption spectrum changes caused by solvent effects has been researched by several scientists 1–4. One example is the solvatochromic transition in conformation of the Si main chain in poly[bis(4‐propoxybutyl)silylene] (PPBS) 1 (see Fig.…”

Layer-by-layer assembly of intact polydiacetylene vesicles with retained chromic properties

“…Polydiacetylenes can be prepared by topochemical polymerization of monomeric diacetylenes in numerous forms: bulk solids [18,19], self-assembled films [20,21], and vesicles suspended in liquids [22,23]. Aqueous suspended polydiacetylene vesicles are generally produced from photopolymerization of vesicles formed from monomeric diacetylene lipids.…”

Chromic Transitions in Polydiacetylenes: Poly(1-(3-Quinolyl)-4-((Ch2)noconhch2oco(ch2)3ch3)-Buta-1,3-Diyne)

“…In recent years, synthesis of soluble polydiacetylenes with rigid aryl groups directly attached to the backbone has been achieved [20][21][22][23]. Aryl substituents directly attached to the conjugated backbone have been shown to modulate the properties of the PDAs through high π electron density per repeat unit and potential for π conjugation with the backbone [20].…”

“…Aryl substituents directly attached to the conjugated backbone have been shown to modulate the properties of the PDAs through high π electron density per repeat unit and potential for π conjugation with the backbone [20]. Solvatochromic and thermochromic studies of such polydiacetylenes exhibit characteristics indicating distinctive influence of the aryl substituent on the coiling behavior of the polydiacetylene backbone [22][23][24]. Thus, for poly(1,4-bis(3-quinolyl)buta-1,3-diyne) abbreviated as PDQ, a PDA with symmetrically substituted rigid 3-quinolyl pendant group, unusually low energy electronic transitions were observed in phenol (λ max~6 56 nm), phenol-non solvent (λ max~6 94, ethanol, DMF, toluene etc.)…”