Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 50, Pages 18003-18010Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201909048
Keywords
amphidynamic crystals; gold(I) complex; luminescent materials; molecular rotors; Saliente Effekte
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Funding
- MEXT (Japan) program Strategic Molecular and Materials Chemistry through Innovative Coupling Reactions of Hokkaido University
- Building of Consortia for the Development of Human Resources in Science and Technology, Program for Fostering Researchers for the Next Generation
- JSPS KAKENHI [JP15H03804, JP16H06034, JP17H05134, JP17H05344, JP17H06370, JP19K23618]
- National Science Foundation [DMR-1700471, MRI-1532232]
- MRSEC Program of the NSF [DMR 1720256]
- NSF
- [JP17J01104]
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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.
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