TY - JOUR
T1 - Mechanochemical Enhancement of the Structural Stability of Pseudorotaxane Intermediates in the Synthesis of Rotaxanes
AU - Kwon, Tae Woo
AU - Song, Bo
AU - Nam, Kwan Woo
AU - Stoddart, J. Fraser
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/7/20
Y1 - 2022/7/20
N2 - Mechanochemical syntheses of rotaxanes have attracted considerable attention of late because of the superior reaction rates and higher yields associated with their production compared with analogous reactions carried out in solution. Previous investigators, however, have focused on the demonstration of the mechanochemical syntheses of rotaxanes per se, rather than on studying the solid-phase host-guest molecular interplay related to their rapid formation and high yields. In this investigation, we attribute the lower yields of rotaxanes prepared in solution to the limited concentration and a desolvation energy penalty that must be compensated for by host-guest interactions during complexation that precedes the templation leading to rotaxane formation. It follows that, if the desolvation energy can be removed and higher concentrations can be attained, even weak host-guest interactions can drive the complexation of host and guest molecules efficiently. In order to test this hypothesis, we chose two host-guest pairs of permethylated pillar[5]arene/1,6-diaminohexane and permethylated pillar[5]arene/2,2′-(ethylenedioxy)bis(ethylamine) for the simple reason that they exhibit extremely low binding constants (2.7 ± 0.4 M-1when 1,6-diaminohexane is the guest and <0.1 M-1when 2,2′-(ethylenedioxy)bis(ethylamine) is the guest in CDCl3; i.e., ostensibly no pseudorotaxane formation is observed). We argue that the amount of pseudorotaxanes formed in the solid state is responsive to mechanical treatments or otherwise and changes in temperature during stoppering reactions. Compared to the amount of pseudorotaxanes that can be obtained in solution, large quantities of pseudorotaxanes are formed in the solid state because of concentration and desolvation effects. This mechanochemical enhancement of pseudorotaxane formation is referred to as a self-correction in the current investigation. Rotaxanes based on permethylated pillar[5]arene/1,6-diaminohexane and permethylated pillar[5]arene/2,2′-(ethylenedioxy)bis(ethylamine) have been synthesized in much higher yields compared to those obtained in solution, aided and abetted by self-correction effects during mechanical treatments and heating at a mild temperature of 50 °C.
AB - Mechanochemical syntheses of rotaxanes have attracted considerable attention of late because of the superior reaction rates and higher yields associated with their production compared with analogous reactions carried out in solution. Previous investigators, however, have focused on the demonstration of the mechanochemical syntheses of rotaxanes per se, rather than on studying the solid-phase host-guest molecular interplay related to their rapid formation and high yields. In this investigation, we attribute the lower yields of rotaxanes prepared in solution to the limited concentration and a desolvation energy penalty that must be compensated for by host-guest interactions during complexation that precedes the templation leading to rotaxane formation. It follows that, if the desolvation energy can be removed and higher concentrations can be attained, even weak host-guest interactions can drive the complexation of host and guest molecules efficiently. In order to test this hypothesis, we chose two host-guest pairs of permethylated pillar[5]arene/1,6-diaminohexane and permethylated pillar[5]arene/2,2′-(ethylenedioxy)bis(ethylamine) for the simple reason that they exhibit extremely low binding constants (2.7 ± 0.4 M-1when 1,6-diaminohexane is the guest and <0.1 M-1when 2,2′-(ethylenedioxy)bis(ethylamine) is the guest in CDCl3; i.e., ostensibly no pseudorotaxane formation is observed). We argue that the amount of pseudorotaxanes formed in the solid state is responsive to mechanical treatments or otherwise and changes in temperature during stoppering reactions. Compared to the amount of pseudorotaxanes that can be obtained in solution, large quantities of pseudorotaxanes are formed in the solid state because of concentration and desolvation effects. This mechanochemical enhancement of pseudorotaxane formation is referred to as a self-correction in the current investigation. Rotaxanes based on permethylated pillar[5]arene/1,6-diaminohexane and permethylated pillar[5]arene/2,2′-(ethylenedioxy)bis(ethylamine) have been synthesized in much higher yields compared to those obtained in solution, aided and abetted by self-correction effects during mechanical treatments and heating at a mild temperature of 50 °C.
UR - http://www.scopus.com/inward/record.url?scp=85134720763&partnerID=8YFLogxK
U2 - 10.1021/jacs.2c00515
DO - 10.1021/jacs.2c00515
M3 - Article
C2 - 35797453
AN - SCOPUS:85134720763
SN - 0002-7863
VL - 144
SP - 12595
EP - 12601
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 28
ER -