Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals. (24th October 2019)

• Record Type: Journal Article
• Authors: Jin, Mingoo; Yamamoto, Sho; Seki, Tomohiro; Ito, Hajime; Garcia‐Garibay, Miguel A.
• Is Part Of: Angewandte Chemie. Volume 131:Number 50(2019)
• Page Start: 18171
• Page End: 18178
• Publication Date: 2019-10-24
• Subjects: Amphidynamische Kristalle -- Gold(I)-Komplexe -- Lumineszente Materialien -- Molekulare Rotoren; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201909048
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : Springende Kristalle : Multifunktionelle amphidynamische Kristalle basierend auf hantelförmigen Gold(I)‐Komplexen sind durch Bewegung auf molekularem und makroskopischem Maßstab charakterisiert. Die makroskopische Bewegung findet als thermosaliente Kristallbewegung oder „Springen" durch anisotrope thermale Expansion statt. Die Phosphoreszenz der Kristalle korreliert mit der Molekülrotation.