TY - JOUR
T1 - Unusual dynamic stimuli-responsive metallamacrocyclic configurational switches
AU - Kong, Yaqiong
AU - Su, Yan
AU - Qian, Yong
AU - Deeth, Robert J.
AU - Romero-Canelón, Isolda
AU - Su, Zhi
AU - Liu, Hong-Ke
AU - Sadler, Peter J.
PY - 2025/5/27
Y1 - 2025/5/27
N2 - Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(II) metallamacrocycles [Ru(η6-p-cymene)(µ 2-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.
AB - Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(II) metallamacrocycles [Ru(η6-p-cymene)(µ 2-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.
U2 - 10.1016/j.cclet.2025.111375
DO - 10.1016/j.cclet.2025.111375
M3 - Article
SN - 1001-8417
VL - 37
JO - Chinese Chemical Letters
JF - Chinese Chemical Letters
IS - 3
M1 - 111375
ER -