Nan Yu,Yingqiu Zhu,Tingting Wang,Ruihan Lin,Longhua Li,Guowei Yang,Xianglong Liu,Jianghua Li,Junli Wang
Currently, there is not much success in solving the molecular and crystal structures of long-chain metal alkanethiolate complexes [M(SCnH2n+1)m] at the atomic level. Taking Sb(SC16H33)3 (1) as an example, we herein disclose the structural characteristics of long-chain trivalent antimony(III) alkanethiolates Sb(SCnH2n+1)3 (n ≥ 12) by single-crystal X-ray crystallography. Specifically, the Sb atom is three-coordinated by alkanethiolate ligands and a slightly distorted triangular pyramid SbS3 core is formed owing to the unique intramolecular stereochemistry of three alkyl chains, namely, two of them almost parallel aligning and the third chain extending alone around the SbS3 core. We further determine the conformation, spatial orientation and packing density of alkyl chains in 1 along with a comparison to those in other long-chain crystalline systems, and reveal the roles of intermolecular van der Waals and Sb···S secondary interactions in molecular self-assembly, which enables 1 to be a layer-structured molecular crystal with a monoclinic P21/c unit cell. The band structures and the atomic orbital contributions to the valence band maximum and conduction band minimum for 1 have also been evaluated by DFT calculations and rationally correlated with its optical absorption property. This study will help understand and discover new structures and structure−property relations of long-chain chemical systems.
Thermotropic monodomain liquid crystal elastomers (mLCEs) exhibit reversible contractile actuation properties along the collimated direction of mesogens when stimulated by external temperature, similar to those of biological skeletal muscle, and have great potential applications in flexible actuators and artificial muscles. However, the existence of flexible chain segments causes mLCEs to elongate under a small load, making calibration under different loads necessary when they are used as an actuator. In this study, a physical crosslinking point between flexible segments is provided through the introduction of designed long-chain molecules (LHS) containing amide bonds on the main chain of LCEs. The 5% LHS-mLCEs with enhanced anti-strain robustness achieved essentially constant original length over a range of loads (0–0.25 MPa) and maintained a reversible contraction ratio of 39.4%, comparable to biological skeletal muscle. Furthermore, a nonreconfigurable topological structure of a metal electrothermal layer with lossless compression properties was designed and prepared on the surface of mLCEs. The film actuators exhibit higher frequency oscillatory actuation (0.1 Hz 9.2%; 0.2 Hz 6.3%; 0.5 Hz 2%) relative to previously reported actuators, benefitting from the optimized heat dissipation structure of LCEs/Ag/air. This study provides valuable references and ideas for applying thermotropic mLCEs in practice.
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