Supramolecular Double-Helix Formation by Diastereoisomeric Conformations of Configurationally Enantiomeric Macrocycles

被引：0

作者：

机构：

[1] Samanta, Avik

[2] Liu, Zhichang

[3] Nalluri, Siva Krishna Mohan

[4] Zhang, Yu

[5] Schatz, George C.

[6] Stoddart, J. Fraser

来源：

Stoddart, J. Fraser (stoddart@northwestern.edu) | 1600年 / American Chemical Society卷 / 138期

关键词：

Solid-state superstructures; resulting from assemblies programmed by homochirality; are attracting considerable attention. In addition; artificial double-helical architectures are being investigated; especially in relation to the ways in which homochiral small molecules can be induced to yield helical forms as a result of chiral induction. Herein; we report the highly specific self-assembly upon crystallization of a double-helical superstructure from an enantiopure macrocyclic dimer which adopts two diastereoisomeric conformations in a molar ratio of 1.5:1 in dimethyl sulfoxide. These two conformational diastereoisomers self-organize - and self-sort - in the crystalline phase in equimolar proportions to form two single-handed helices which are complementary to each other; giving rise to the assembly of a double helix that is stabilized by intermolecular [C-H···O] and stacking interactions. The observed self-sorting phenomenon occurs on going from a mixed-solvent system containing two equilibrating conformational diastereoisomers; presumably present in unequal molar proportions; into the solid state. The diastereoisomeric conformations are captured upon crystallization in a 1:1 molar ratio in the double-helical superstructure; whose handedness is dictated by the choice of the enantiomeric macrocyclic dimer. The interconversion of the two conformational diastereoisomers derived from each configurationally enantiomeric macrocycle was investigated in CD3SOCD3 solution by variable-temperature 1H NMR spectroscopy (VT NMR) and circular dichroism (VT CD). The merging of the resonances for the protons corresponding to the two diastereoisomers at a range of coalescence temperatures in the VT NMR spectra and occurrence of the isosbestic points in the VT CD spectra indicate that the two diastereoisomers are interconverting slowly in solution on the 1H NMR time scale but rapidly on the laboratory time scale. To the best of our knowledge; the self-assembly of such solid-state superstructures from two conformational diastereoisomers of a homochiral macrocycle is a rare; if not unique; occurrence. © 2016 American Chemical Society;

D O I：

暂无

中图分类号：

学科分类号：

摘要：

Journal article (JA)

引用

共 35 条

[1] Supramolecular Double-Helix Formation by Diastereoisomeric Conformations of Configurationally Enantiomeric Macrocycles
Samanta, Avik
Liu, Zhichang
Nalluri, Siva Krishna Mohan
Zhang, Yu
Schatz, George C.
Stoddart, J. Fraser
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (43) : 14469 - 14480
[2] Double helices of opposite chiralities generated from diastereoisomeric conformations of configurationally enantiomeric macrocycles
Samanta, Avik
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2016, 252
[3] Supramolecular Organogels Formed through Complementary Double-Helix Formation
Banno, Motonori
Wu, Zong-Quan
Makiguchi, Wataru
Furusho, Yoshio
Yashima, Eiji
CHEMPLUSCHEM, 2014, 79 (01): : 35 - 44
[4] Halogen bonding-driven formation of supramolecular macrocycles and double helix
Chuan-Zhi Liu
Satish Koppireddi
Hui Wang
Dan-Wei Zhang
Zhan-Ting Li
Chinese Chemical Letters, 2019, 30 (05) : 953 - 956
[5] Halogen bonding-driven formation of supramolecular macrocycles and double helix
Liu, Chuan-Zhi
Koppireddi, Satish
Wang, Hui
Zhang, Dan-Wei
Li, Zhan-Ting
CHINESE CHEMICAL LETTERS, 2019, 30 (05) : 953 - 956
[6] KINETIC-STUDY OF DOUBLE-HELIX FORMATION AND DOUBLE-HELIX DISSOCIATION OF POLYADENYLIC-ACID
MAGGINI, R
SECCO
VENTURINI, M
DIEBLER, H
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1994, 90 (16): : 2359 - 2363
[7] Double-Helix Supramolecular Nanofibers Assembled from Negatively Curved Nanographenes
Kato, Kenta
Takaba, Kiyofumi
Maki-Yonekura, Saori
Mitoma, Nobuhiko
Nakanishi, Yusuke
Nishihara, Taishi
Hatakeyama, Taito
Kawada, Takuma
Hijikata, Yuh
Pirillo, Jenny
Scott, Lawrence T.
Yonekura, Koji
Segawa, Yasutomo
Itami, Kenichiro
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2021, 143 (14) : 5465 - 5469
[8] A supramolecular double-helix based on complementary phosphate-guanidinium pairing
Thiele, Maike
Octa-Smolin, Frescilia
Thoelke, Simon
Woelper, Christoph
Linders, Jurgen
Mayer, Christian
Haberhauer, Gebhard
Niemeyer, Jochen
CHEMICAL COMMUNICATIONS, 2021, 57 (77) : 9842 - 9845
[9] A metallo-supramolecular double-helix containing a major and a minor groove
Hannon, MJ
Painting, CL
Alcock, NW
CHEMICAL COMMUNICATIONS, 1999, (20) : 2023 - 2024
[10] Enantiodifferentiating Photodimerization of a 2,6-Disubstituted Anthracene Assisted by Supramolecular Double-Helix Formation with Chiral Amines
Urushima, Akio
Taura, Daisuke
Tanaka, Makoto
Horimoto, Naomichi
Tanabe, Junki
Ousaka, Naoki
Mori, Tadashi
Yashima, Eiji
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (19) : 7478 - 7486

← 1 2 3 4 →