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Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals
Author(s) -
Jin Mingoo,
Yamamoto Sho,
Seki Tomohiro,
Ito Hajime,
GarciaGaribay Miguel A.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201909048
Subject(s) - anisotropy , intermolecular force , rotation around a fixed axis , molecular dynamics , chemical physics , chromophore , materials science , crystal (programming language) , molecular motor , phosphorescence , molecular physics , chemistry , molecule , nanotechnology , computational chemistry , classical mechanics , physics , photochemistry , optics , organic chemistry , computer science , fluorescence , programming language
Herein we report a crystalline molecular rotor with rotationally modulated triplet emission that displays macroscopic dynamics in the form of crystal moving and/or jumping, also known as salient effects. Molecular rotor 2 with a central 1,4‐diethynyl‐2,3‐difluorophenylene rotator linked to two gold(I) nodes, crystalizes as infinite 1D chains through intermolecular gold(I)–gold(I) interactions. The rotational motion changes the orientation of the central phenylene, changing the electronic communication between adjacent chromophores, and thus the emission intensities. Crystals of 2 showed the large and reversible thermal expansion/compression anisotropy, which accounts for 1) a nonlinear Arrhenius behavior in molecular‐level rotational dynamics, which correlates with 2) changes in emission, and determines 3) the macroscopic crystal motion. A molecular rotor analogue 3 has properties similar to those of 2 , suggesting a generalized way to control mechanical properties at molecular and macroscopic scales.