Ralph Ugalino, Kosuke Yamazoe, Jun Miyawaki, Hisao Kiuchi, Naoya Kurahashi, Yuka Kosegawa, Yoshihisa Harada
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引用次数: 0
摘要
金属有机框架(MOFs)在温度和客体吸附的诱导下表现出结构灵活性,某些 MOFs 在窄孔相和大孔相之间的结构呼吸转变就证明了这一点。有人认为,软模式在高温下通过增强振动动力学来推动这种孔隙呼吸。在这项研究中,对 MIL-53(Al)MOF 进行了氧 K 边共振 X 射线发射光谱分析,以选择性地探测配体羧酸位点伴随孔隙呼吸动力学的电子扰动,从而实现金属与配体的相互作用。研究发现,温度诱导的振动动力学涉及羧酸氧孤对轨道的非对称构型和对称构型之间的占位切换,通过这种切换,羧酸氧位点周围的电子密度被重新分配,金属与配体之间的相互作用也得到了调整。反过来,水的吸附还涉及到π轨道的额外扰动,这在仅由温度引起的结构变化中是观察不到的。
The role of carboxylate ligand orbitals in the breathing dynamics of a metal-organic framework by resonant X-ray emission spectroscopy.
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.
期刊介绍:
Synchrotron radiation research is rapidly expanding with many new sources of radiation being created globally. Synchrotron radiation plays a leading role in pure science and in emerging technologies. The Journal of Synchrotron Radiation provides comprehensive coverage of the entire field of synchrotron radiation and free-electron laser research including instrumentation, theory, computing and scientific applications in areas such as biology, nanoscience and materials science. Rapid publication ensures an up-to-date information resource for scientists and engineers in the field.