Is the Smallest Molecular Trefoil Knot Actually the Tightest One?

W Wei‐Tao Xu (School of Chemistry and Molecular Engineering East China Normal University Shanghai China) C Chenxing Guo (College of Chemistry and Environmental Engineering Shenzhen University Shenzhen Guangdong 518060 China) Y Yefei Jiang (Shanghai Key Laboratory of Green Chemistry and Chemical Processes State Key Laboratory of Petroleum Molecular and Process Engineering School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 China) W Wei‐Jian Li (Shanghai Key Laboratory of Green Chemistry and Chemical Processes State Key Laboratory of Petroleum Molecular and Process Engineering School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 China) X Xiao‐Qin Xu (School of Chemistry and Molecular Engineering East China Normal University Shanghai China) X Xue Li S Siqi Luo L Lianrui Hu (Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering) X Xiujun Yu (State Key Laboratory of Radio Frequency Heterogeneous Integration, College of Chemistry and Environmental Engineering) X Xiaopeng Li (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China) H Hai‐Bo Yang (School of Chemistry and Molecular Engineering East China Normal University Shanghai China) W Wei Wang

Abstract

Abstract Tightness engineering has evolved as an efficient strategy for the design of knotted, woven, and entangled molecules and materials with desired properties and functions since tightness is a primary parameter that determines the property of a knotted strand. However, as an attractive topic that inspires mathematicians, physicists, chemists, and biologists, whether the smallest knot is exactly the tightest one remains unaddressed experimentally. To tackle this challenge, a series of organic trefoil knots with the backbone‐atom as short as 70 have been successfully synthesized by developing a new modular self‐assembly approach in this study. To our great surprise, with the help of gradient tandem mass spectrometry, the quantitative tightness evaluation suggested that the molecular trefoil knot with a backbone crossing ratio (BCR) of 24.0 is even tighter than the one with a BCR of 23.3 (i.e., the smallest organic trefoil knot with the shortest ropelength synthesized so far), thus demonstrating an unexpected yet interesting odd‐even effect to enhance the understanding of the tightness regulation of molecular knots.

Article Details

Volume / Issue Vol. 64, Issue 35
Published August 25, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (12)

W

Wei‐Tao Xu

School of Chemistry and Molecular Engineering East China Normal University Shanghai China

C

Chenxing Guo

College of Chemistry and Environmental Engineering Shenzhen University Shenzhen Guangdong 518060 China

Y

Yefei Jiang

Shanghai Key Laboratory of Green Chemistry and Chemical Processes State Key Laboratory of Petroleum Molecular and Process Engineering School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 China

W

Wei‐Jian Li

Shanghai Key Laboratory of Green Chemistry and Chemical Processes State Key Laboratory of Petroleum Molecular and Process Engineering School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 China

X

Xiao‐Qin Xu

School of Chemistry and Molecular Engineering East China Normal University Shanghai China

X

Xue Li

S

Siqi Luo

L

Lianrui Hu

Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering

X

Xiujun Yu

State Key Laboratory of Radio Frequency Heterogeneous Integration, College of Chemistry and Environmental Engineering

X

Xiaopeng Li

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China

H

Hai‐Bo Yang

School of Chemistry and Molecular Engineering East China Normal University Shanghai China

W

Wei Wang