Citation: Yaqiong Kong, Yan Su, Yong Qian, Robert J. Deeth, Isolda Romero-Canelón, Zhi Su, Hong-Ke Liu, Peter J. Sadler. Unusual dynamic stimuli-responsive metallamacrocyclic configurational switches[J]. Chinese Chemical Letters, ;2026, 37(3): 111375. doi: 10.1016/j.cclet.2025.111375 shu

Unusual dynamic stimuli-responsive metallamacrocyclic configurational switches

Yaqiong Kong ^{a, d, 1} ,
Yan Su ^{a, 1} ,
Yong Qian ^a ,
Robert J. Deeth ^b ,
Isolda Romero-Canelón ^c ,
Zhi Su ^{a, *,} ,
Hong-Ke Liu ^{a, *,} ,
Peter J. Sadler ^{b, *,}

a.
College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
b.
Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom
c.
School of Pharmacy, Institute of Clinical Sciences, University of Birmingham, Birmingham B15 2TT, United Kingdom
d.
College of Chemistry and Materials Engineering, Chaohu University, Chaohu 238024, China

zhisu@njnu.edu.cn

liuhongke@njnu.edu.cn

P.J.Sadler@warwick.ac.uk

Received Date: 7 January 2025
Revised Date: 12 May 2025
Accepted Date: 26 May 2025
Available Online: 27 May 2025

Figures(6)

Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(Ⅱ) metallamacrocycles [Ru(η⁶-p-cymene)(µ₂-m-bitmb)Cl]₂·2X, m-bitmb = 1,3,5-trimethyl-2,4-di(imidazole-1-ylmethyl)benzene, X = Cl^- (1·2Cl), NO₃^- (1·2NO₃), CF₃SO₃^- (1·2CF₃SO₃), PF₆^- (1·2PF₆), or BF₄^- (1·2BF₄). X-ray crystal structures reveal 1·2Cl in boat and chair conformations, 1·2NO₃ in twist-boat and chair conformations, and 1·2CF₃SO₃ in a chair conformation. Chair/boat isomers of mono- and bis-DMSO adducts from 1·2Cl, 1·2CF₃SO₃ or 1·2NO₃ in DMSO/H₂O were separated and characterized. Slow anion-dependent interconversion of configurational isomers was observed in solution. Ligand field molecular mechanics and density functional theory calculations suggest an unusual macrochelate ring-opening isomerization mechanism. Such dynamic stimuli-responsive configurational changes offer scope for design of metallocycles for induced-fit recognition of biological targets.
- Metallacycles,
- Coordination mode,
- Ruthenium isomer,
- Structure elucidation,
- Configuration
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