DOI: 10.5061/dryad.nvx0k6f4c
title: A molecular machine directs the synthesis of a catenane

description: Precise mechanical manipulation of molecules is inherently difficult due
 to random thermal motion. While directed movement on the molecular scale
 has been achieved, using it to impose specific, especially energetically
 disfavored, shapes on molecules and construct mechanically interlocked
 structures remains a fundamental challenge. Here, we report the synthesis
 of a catenane enabled by a molecular motor that winds molecular strands
 into discrete entangled structures, each defined by a specific number of
 mechanical crossings. Light energy drives unidirectional motor rotation,
 enabling path-dependent control over a sequence of thermodynamically
 disfavored yet mechanically distinct and kinetically stable winding
 states, which are covalently captured and subsequently released to yield a
 catenane. This machine-directed approach offers a general proof-of-concept
 strategy for the template-free construction of mechanically interlocked
 molecules.
description: # A molecular machine directs the synthesis of a catenane Dataset DOI:
 [10.5061/dryad.nvx0k6f4c](10.5061/dryad.nvx0k6f4c) ## Description of the
 data and file structure The repository contains all the raw NMR data that
 was used for the preparation of the manuscript and supporting material.
 The main directory contains four folders: 1\) The full NMR
 characterization of all synthesized molecules can be found in
 "NMR_Compounds". 2\) The NMR data of the covalently captured
 stable helicity winding isomers (Zs)-0, (Es)-1, (Zs)-2, and (Es)-3 can be
 found in "NMR_Covalent Capture". 3\) Diffusion-ordered
 spectroscopy (DOSY) NMR of the stable helicity winding isomers (Zs)-0,
 (Es)-1, (Zs)-2, and (Es)-3, the references macrocycles ((Zs)-MM, (Es)-MM,
 OM) and the catenanes ((Zs)-Catenane and (Es)-Catenane) can be found in
 "NMR_DOSY". 4\) The NMR investigation of the winding mechanism
 and winding states of machine (Zs)-0 can be found in "NMR_Winding
 Isomers". In each main folder, the subfolder of each performed
 experiment (e.g., NMR_Compounds/S22_Zs-Catenane) can be opened via drag
 & drop into the MestReNova or TopSpin software. ### Files and
 variables #### File: NMR_Data.zip **Description:**  Each following bullet
 point starts with the title of the experiments, followed by a short
 description of the dataset. ## NMR_Compounds: ##### NMR data of all
 synthesized molecules (S1-S23) (1H, 13C, COSY, HSQC, HMBC, 19F if
 applicable) * "S1_C12DiolTether" to "S23_Es-Catenane"
 - NMR dataset of the compounds that are presented in the synthesis chapter
 (chapter 2) of the supporting material ##### NMR data of the mixtures of
 (Zs)-MM/OM and (Es)-MM/OM (1H, 19F) * "(Es)-MM and OM mixture" -
 1H and 19F NMR data shown in fig. S28 and S29 * "(Zs)-MM and OM
 mixture" - 1H and 19F NMR data shown in fig. S28 and S29 ##
 NMR_Covalent Capture: ##### NMR data of the covalently captured winding
 isomers (Zs)-0, (Es)-1, (Zs)-2, (Es)-3 * "hemz1211-WTO-ZSO" - 1H
 and 19F NMR data of covalently captured (Zs)-0 isomer shown in fig. S23 *
 "hemz1212-WTO-ES1" - 1H and 19F NMR data of covalently captured
 (Es)-1 isomer shown in fig. S23 * "hemz1213-WTO-ZS2" - 1H and
 19F NMR data of covalently captured (Zs)-2 isomer shown in fig. S23 *
 "hemz1214-WTO-ES3" - 1H and 19F NMR data of covalently captured
 (Es)-3 isomer shown in fig. S23 ## NMR_DOSY: ##### 1H-DOSY NMR data of the
 winding isomers (Zs)-0, (Es)-1, (Zs)-2, (Es)-3, the catenanes, and the
 reference macrocycles (Zs)-MM, (Es)-MM, and OM *
 "heWTO-Zs0-DOSY" - DOSY NMR data of (Zs)-0 *
 "heWTO-Es1-DOSY2" - DOSY NMR data of (Es)-1 *
 "heWTO-Zs2-DOSY2" - DOSY NMR data of (Zs)-2 *
 "heWTO-Es3-DOSY2" - DOSY NMR data of (Es)-3 *
 "heWTO-ZsCat-DOSY" - DOSY NMR data of (Zs)-Catenane shown in
 fig. S35 * "heWTO-EsCat-DOSY" - DOSY NMR data of (Es)-Catenane
 shown in fig. S36 * "heWTO-226-E-DOSY" - DOSY NMR data of
 (Es)-MM shown in fig. S34 * "heWTO-226-z" - DOSY NMR data of
 (Zs)-MM shown in fig. S33 * "heWTO-243-DOSY" - DOSY NMR data of
 OM shown in fig. S32 ## **NMR_Winding Isomers:** ##### NMR data for
 winding sequence of (Zs)-0 (1H, 19F) * "20C Winding Sequence
 19F" - shown in fig. S4 * "40C Winding Sequence 1H" - shown
 in fig. S3 * "-30C Winding Sequence 19F" - shown in fig. S5
 ##### NMR data for rotational cycle of benzoylated (Zs)-MM (1H) *
 "(Zs)-MM Rotational Cycle" - 1H NMR data of the 360° rotational
 cycle of benzoylated motor macrocycle (Zs)-MM/S20 shown in fig. S15 #####
 NMR data of winding isomers (Zs)-0, (Es)-1, (Zs)-2, (Es)-3 (1H, 13C, COSY,
 HSQC, HMBC, ROESY) * "Zs-0" - 1D and 2D NMR characterization of
 (Zs)-0, ROESY shown in fig. S19 * "Es-1" - 1D and 2D NMR
 characterization of (Es)-1, ROESY shown in fig. S21 * "Zs-2" -
 1D and 2D NMR characterization of (Zs)-2, ROESY shown in fig. S20 *
 "Es-3" - 1D and 2D NMR characterization of (Es)-3, ROESY shown
 in fig. S22 * "Es-3 and Zm-4 at -10C and 40C" - 1H NMR data of
 (Es)-3 and (Zm)-4 at -10 °C and 40 °C shown in fig. S12 and S13 #####
 VT-NMR experiment of (Es)-3 (1H) * "Es-3 VT Experiment" - 1H NMR
 data of (Es)-3 from -10 °C to 80 °C shown in fig. S14 ## Code/software The
 NMR data were evaluated with MestReNova Version 11.0.4-18998 or TopSpin
 Version 4.5.0. ## Access information NA