期刊
ACS APPLIED MATERIALS & INTERFACES
卷 12, 期 42, 页码 47921-47938出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.0c12726
关键词
aggregation-induced emission (AIE); Forster resonance energy transfer (FRET); photo-switchable [2]rotaxane; spiropyran; tetraphenylethylene
资金
- Ministry of Science and Technology, Taiwan, ROC
- Ministry of Science and Technology, Taiwan [MOST106-2113-M-009-012-MY3, MOST107-2221-E-009-043-MY2, MOST108-3017-F-009-004]
- Center for Emergent Functional Matter Science of the National Chiao Tung University from The Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) in Taiwan
- National Science Foundation [CHE-1751370]
- National Institute of General Medical Sciences (NIGMS) of the National Institute of Health [R35GM133548]
- NSF [MRI-1531814]
A series of novel photo-switchable [2]rotaxanes (i.e., Rot-A-SP and Rot-B-SP before and after shuttling controlled by acid-base, respectively) containing one spiropyran (SP) unit (as a photochromic stopper) on the axle and two tetraphenylethylene (TPE) units on the macrocycle were synthesized via click reaction. Upon UV/visible light exposure, both mono-fluorophoric rotaxanes Rot-A-SP and Rot-B-SP with the closed form (i.e., non-emissive SP unit) could be transformed into the open form (i.e., red-emissive merocyanine (MC) unit) to acquire their respective bi-fluorophoric Rot-A-MC and Rot-B-MC reversibly. The aggregation-induced emission (AIE) properties of bi-fluorophoric TPE combined with MC AIEgens of these designed rotaxanes and mixtures in semi-aqueous solutions induced interesting ratiometric photoluminescence (PL) and Forster resonance energy transfer (FRET) behaviors, which were further investigated and verified by dynamic light scattering (DLS), X-ray diffraction (XRD), and time-resolved photoluminescence (TRPL) measurements along with theoretical studies. Accordingly, in contrast to the model axle (Axle-MC) and the analogous mixture (Mixture-MC, containing the axle and macrocycle components in a 1:1 molar ratio), more efficient FRET behaviors and stronger red PL emissions were obtained from dual-AIEgens between a blue-emissive TPE donor (PL emission at 468 nm) and a red-emissive MC acceptor (PL emission at 668 nm) in both novel photo-switchable [2]rotaxanes Rot-AMC and Rot-B-MC under various external modulations, including water content, UV/Vis irradiation, pH value, and temperature. Furthermore, the reversible fluorescent photo-patterning applications of Rot-A-SP in a powder form and a solid film with excellent photochromic and fluorescent behaviors are first investigated in this report.
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