Temperature‐Triggered Structural Dynamics of Non‐Coordinating Guest Moieties in a Fluorescent Actinide Polyrotaxane Framework

We present here the synthesis of a novel fluorescent actinide polyrotaxane compound URCP1 through the utilization of an end‐cutting pseudorotaxane precursor with only the cucurbit[6]uril (CB[6]) macrocyclic components acting as linking struts. The non‐coordinating guest motif in the obtained polyrot...

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Bibliographic Details
Published in:Chemistry : a European journal 2021-06, Vol.27 (34), p.8730-8736
Main Authors: Li, Fei‐ze, Geng, Jun‐shan, Hu, Kong‐qiu, Zeng, Li‐wen, Wang, Jing‐yang, Kong, Xiang‐he, Liu, Ning, Chai, Zhi‐fang, Mei, Lei, Shi, Wei‐qun
Format: Article
Language:English
Subjects:
actinide-coordination compounds
Aqueous solutions
Cations
Chemistry
Crystallography
fluorescent detection
Fluorescent indicators
Iron
Photoluminescence
Photons
pseudorotaxane
structure dynamics
Struts
supramolecular chemistry
Temperature
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Summary:We present here the synthesis of a novel fluorescent actinide polyrotaxane compound URCP1 through the utilization of an end‐cutting pseudorotaxane precursor with only the cucurbit[6]uril (CB[6]) macrocyclic components acting as linking struts. The non‐coordinating guest motif in the obtained polyrotaxane, with increased freedom and structural flexibility, can display intriguing temperature‐triggered conformational variations inside the cavity of CB[6], which was clearly evidenced by crystallographic snapshots at different temperatures. Notably, this observation of temperature‐triggered structural dynamics in URCP1 represents the first report of actinide polyrotaxane with such feature in solid‐state. Moreover, URCP1 has a high photoluminescence quantum yield (PLQY) of 49.8 %, comparable to other luminescent uranyl compounds, and can work as a fluorescent probe to selectively detect Fe3+ over other eight competing cations in aqueous solution, with the limit of detection being as low as 4.4×10−3 ppm. A new fluorescent uranyl‐coordination polyrotaxane only connected by macrocyclic host has been constructed. The non‐coordinating guest (C7BPy) in the obtained polyrotaxane shows thermal displacement and dynamic conformational variations with temperature increasing from 150 to 300 K. Meanwhile, this polyrotaxene can selectively detect Fe3+ over other eight competing cations in aqueous solution, with the limit of Fe3+ detection as low as 4.4×10−3 ppm.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202100614