原子轨道
羧酸盐
配体(生物化学)
光谱学
金属
动力学(音乐)
化学
X射线
光化学
发射光谱
材料科学
结晶学
物理
立体化学
光学
电子
谱线
有机化学
生物化学
受体
量子力学
天文
声学
作者
Ralph Ugalino,Kazuaki Yamazoe,Jun Miyawaki,Hisao Kiuchi,Naoya Kurahashi,Yuka Kosegawa,Yoshihisa Harada
标识
DOI:10.1107/s1600577524000584
摘要
Metal-organic frameworks (MOFs) exhibit structural flexibility induced by temperature and guest adsorption, as demonstrated in the structural breathing transition in certain MOFs between narrow-pore and large-pore phases. Soft modes were suggested to entropically drive such pore breathing through enhanced vibrational dynamics at high temperatures. In this work, oxygen K -edge resonant X-ray emission spectroscopy of the MIL-53(Al) MOF was performed to selectively probe the electronic perturbation accompanying pore breathing dynamics at the ligand carboxylate site for metal–ligand interaction. It was observed that the temperature-induced vibrational dynamics involves switching occupancy between antisymmetric and symmetric configurations of the carboxylate oxygen lone pair orbitals, through which electron density around carboxylate oxygen sites is redistributed and metal–ligand interactions are tuned. In turn, water adsorption involves an additional perturbation of π orbitals not observed in the structural change solely induced by temperature.
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