Sequential Block Copolymer Self-Assemblies Controlled by Metal-Ligand Stoichiometry.
While numerous efforts have been devoted to developing easy-to-use probes based on block copolymers for detecting analytes due to their advantages in the fields of self-assembly and sensing, a progressive response on block copolymers in response to a continuing chemical event is not readily achievable. Herein, we report the self-assembly of a 4-piperazinyl-1,8-naphthalimide based functional block copolymer (PS-b-PN), whose self-assembly and photophysics can be controlled by the stoichiometry-dependent metal-ligand interaction upon the side chain. The work takes advantages of (1) stoichiometry-controlled coordination-structural transformation of the piperazinyl moiety on PS-b-PN toward Fe(3+) ions, thereby resulting in a shrinkage-expansion conversion of the self-assembled nanostructures in solution as well as in thin film, and (2) stoichiometry-controlled competition between photoinduced electron transfer and spin-orbital coupling process upon naphthalimide fluorophore leading to a boost-decline emission change of the system. Except Fe(3+) ions, such a stoichiometry-dependent returnable property cannot be observed in the presence of other transition ions. The strategy for realizing the dual-channel sequential response on the basis of the progressively alterable nanomorphologies and emissions might provide deeper insights for the further development of advanced polymeric sensors.
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University , Shanghai 200433, China.
Liyuan
L
Yin
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University , Shanghai 200433, China.
Hongwei
H
Wu
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University , Shanghai 200433, China.
Mingjie
M
Zhu
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai University of Electric Power , Shanghai 200090, China.
Qi
Q
Zou
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University , Shanghai 200433, China.
Qiang
Q
Yan
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University , Shanghai 200433, China.|Department of Chemistry, Columbia University , New York, New York 10027, United States.
Liangliang
L
Zhu