Highly selective synthesis and near-infrared photothermal response of heterometallic double trefoil knot and D-type [2]catenanes  

作　　者：Ying Zhao Jian-Xin Yang Yin-Hang Chai Yao He Peng Wang Francisco Aznarez Bo Li Li-Long Dang Lu-Fang Ma 

机构地区：[1]College of Chemistry and Chemical Engineering,Luoyang Normal University,Luoyang 471934,China [2]College of Chemical and Pharmaceutical Engineering,Nanyang Normal University,Nanyang 473061,China

出　　处：《Science China Chemistry》2025年第4期1383-1391,共9页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China(22471113,22101108,22171123);the Natural Science Foundation of Henan Province(242300421139,232300421232);the Science and Technology Innovation Talent Program of the University in Henan Province(25HASTIT001).

摘　　要：The selective construction of sophisticated supramolecular topologies has always attracted the remarkable attention of researchers.Thus;various molecular knots and catenanes have recently been reported and were obtained either accidentally or by following a previously planned synthetic strategy.Herein;we introduce a series of supramolecular topologies including double trefoil knot(1);trefoil knot(2)and[2]catenanes(4;5);which were prepared via an elaborated self-assembly strategy by using half-sandwich units based on a flexible pyridyl linker L1.The formation of all the structures has been confirmed by single crystal X-ray diffraction analysis and NMR spectroscopy;and ESI-MS.Remarkably;the central potassium ion of 1 coordinates six oxygen atoms belonging to six amide groups from two trefoil segments.The double trefoil knot 1 and[2]catenanes 4;5 are stabilized by parallel-displacedπ···πstacking interactions(of interlayer distance 3.34-3.82?)between the pyridyl fraction and phenyl moieties of three ligands L1;and by edge-to-face-type CH···πinteractions(2.64-2.83?)between Bi Bz Im conjugated planes and phenyl hydrocarbon bond.Interestingly;the addition/removal of potassium ions resulted in topological transformation between the double trefoil knot 1 and the trefoil knot 2.In addition;the addition of DMF-d7 to a methanolic solution of the double trefoil knot 1 induced its structural conversion into the metallamacrocycle 3.NIR photothermal studies of 1;4;and 5 showed different photothermal responses in solid and solution states.Thus;the photothermal conversion efficiencies of 4;and 5 were within the limit of 16.8%-45.1%based on different power areas;the number and the fashion ofπ···πstacking interactions can directly affect the photothermal conversion efficiency;and EPR experiments confirmed the recorded results.

关 键 词：molecular knots CATENANES half-sandwich complexes coordination-driven self-assembly photothermal conversion 

分 类 号：O641[理学—物理化学]