TY - JOUR
T1 - Adjusting Rotational Behavior of Molecular Rotors by a Rational Tuning of Molecular Structure
AU - Li, Hui Miao
AU - Zhong, Gui Ming
AU - Wu, Shuqi
AU - Sato, Osamu
AU - Zheng, Xiao Yan
AU - Yao, Zi Shuo
AU - Tao, Jun
N1 - Funding Information:
This work was supported by the National Natural Science Foundation of China (22071009, 21701013, 21671161, and 21971016).
Publisher Copyright:
©
PY - 2021/6/7
Y1 - 2021/6/7
N2 - Many crystalline molecular rotors have been developed in the past decades. However, manipulating the rotational gesture that intrinsically controls the physical performance of materials remains a challenge. Herein, we report a series of crystalline rotors whose rotational gestures can be modulated by modifying the structures of molecular stators. In these dynamic crystals, the ox2- (ox2- = oxalate anion) behave as molecular rotators performing axial-free rotation in cavities composed of five complex cations, [MII(en)3]2+ (en = ethylenediamine). The structure of [MII(en)3]2+ that serves as a molecular stator can be tuned by varying the metal center with different ionic radii, consequently altering the chemical environment around the molecular rotator. Owing to the quasi-transverse isotropy of ox2- and multiple hydrogen-bond interactions around it, the molecular rotator exhibits unusual motional malleability, i.e., it can rotate either longitudinally in the compound of ZnII, or with a tilt angle of 42° in the compound of FeII, or even laterally in the compound of CdII. The atypical dynamic behavior demonstrated here provides a new chance for the development of exquisite crystalline molecular rotors with advanced tunable functionalities.
AB - Many crystalline molecular rotors have been developed in the past decades. However, manipulating the rotational gesture that intrinsically controls the physical performance of materials remains a challenge. Herein, we report a series of crystalline rotors whose rotational gestures can be modulated by modifying the structures of molecular stators. In these dynamic crystals, the ox2- (ox2- = oxalate anion) behave as molecular rotators performing axial-free rotation in cavities composed of five complex cations, [MII(en)3]2+ (en = ethylenediamine). The structure of [MII(en)3]2+ that serves as a molecular stator can be tuned by varying the metal center with different ionic radii, consequently altering the chemical environment around the molecular rotator. Owing to the quasi-transverse isotropy of ox2- and multiple hydrogen-bond interactions around it, the molecular rotator exhibits unusual motional malleability, i.e., it can rotate either longitudinally in the compound of ZnII, or with a tilt angle of 42° in the compound of FeII, or even laterally in the compound of CdII. The atypical dynamic behavior demonstrated here provides a new chance for the development of exquisite crystalline molecular rotors with advanced tunable functionalities.
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U2 - 10.1021/acs.inorgchem.1c00558
DO - 10.1021/acs.inorgchem.1c00558
M3 - Article
C2 - 34038634
AN - SCOPUS:85107902912
VL - 60
SP - 8042
EP - 8048
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 11
ER -