Nickel-Ion-Coordinated Reversibly Solvatochromic Polydiacetylene Based on Tubular Assembly of Macrocyclic Diacetylene
- Authors
- Kim, Bubsung; Khazi, Mohammed Iqbal; Kim, Jong-Man
- Issue Date
- Sep-2021
- Publisher
- American Chemical Society
- Citation
- Macromolecules, v.54, no.17, pp.8220 - 8228
- Indexed
- SCIE
SCOPUS
- Journal Title
- Macromolecules
- Volume
- 54
- Number
- 17
- Start Page
- 8220
- End Page
- 8228
- URI
- https://scholarworks.bwise.kr/hanyang/handle/2021.sw.hanyang/141009
- DOI
- 10.1021/acs.macromol.1c01210
- ISSN
- 0024-9297
- Abstract
- Polydiacetylenes (PDAs) present excellent chromogenic characteristics and have been extensively utilized as a sensory polymeric material to design and fabricate colorimetric sensor systems. Herein, we describe a Ni2+-ion-directed reversibly solvatochromic tubular PDA based on macrocyclic diacetylene (MCDA). A dimeric MCDA complex was formed through Ni2+-intercalated coordinative binding with carboxyl groups, which later transform into blue-phase PDA upon UV irradiation. Infrared spectral analysis confirmed the presence of structural water molecules coordinating to central Ni2+, which predicted to fulfill the octahedral geometry. Spectroscopic studies for the reversible blue-red chromatic behavior revealed a very unusual and unprecedented chromatic switching mechanism originating due to localized structural disruption at the Ni2+ coordination site that leads to torsion in the π-conjugated backbone for chromatic changes, in contrast to the typical residual monomeric dissolution-induced mechanism. This unusual behavior can be attributed to the coordinating water molecules, which presents an attractive advantage by creating a hydrophilic pocket at the coordination site and allows interactions with hydrophilic solvents causing structural distortion.
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