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Modelling local structural and electronic consequences of proton and hydrogen-atom uptake in VO2 with polyoxovanadate clusters
Chemical Science ( IF 7.6 ) Pub Date : 2021-08-25 , DOI: 10.1039/d1sc02809j Sourav Chakraborty 1 , Eric Schreiber 1 , Karla R Sanchez-Lievanos 1 , Mehrin Tariq 1 , William W Brennessel 1 , Kathryn E Knowles 1 , Ellen M Matson 1
Chemical Science ( IF 7.6 ) Pub Date : 2021-08-25 , DOI: 10.1039/d1sc02809j Sourav Chakraborty 1 , Eric Schreiber 1 , Karla R Sanchez-Lievanos 1 , Mehrin Tariq 1 , William W Brennessel 1 , Kathryn E Knowles 1 , Ellen M Matson 1
Affiliation
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We report the synthesis and characterisation of a series of siloxide-functionalised polyoxovanadate–alkoxide (POV–alkoxide) clusters, [V6O6(OSiMe3)(OMe)12]n (n = 1−, 2−), that serve as molecular models for proton and hydrogen-atom uptake in vanadium dioxide, respectively. Installation of a siloxide moiety on the surface of the Lindqvist core was accomplished via addition of trimethylsilyl trifluoromethylsulfonate to the fully-oxygenated cluster [V6O7(OMe)12]2−. Characterisation of [V6O6(OSiMe3)(OMe)12]1− by X-ray photoelectron spectroscopy reveals that the incorporation of the siloxide group does not result in charge separation within the hexavanadate assembly, an observation that contrasts directly with the behavior of clusters bearing substitutional dopants. The reduced assembly, [V6O6(OSiMe3)(OMe)12]2−, provides an isoelectronic model for H-doped VO2, with a vanadium(III) ion embedded within the cluster core. Notably, structural analysis of [V6O6(OSiMe3)(OMe)12]2− reveals bond perturbations at the siloxide-functionalised vanadium centre that resemble those invoked upon H-atom uptake in VO2 through ab initio calculations. Our results offer atomically precise insight into the local structural and electronic consequences of the installation of hydrogen-atom-like dopants in VO2, and challenge current perspectives of the operative mechanism of electron–proton co-doping in these materials.
中文翻译：
用多氧钒酸盐簇模拟 VO2 中质子和氢原子吸收的局部结构和电子后果
我们报告了一系列硅氧化物官能化的多氧钒酸盐-醇盐（POV-醇盐）簇的合成和表征，[V 6 O 6 (OSiMe 3 )(OMe) 12 ] n ( n = 1−, 2−)，其用于分别作为二氧化钒中质子和氢原子吸收的分子模型。通过将三氟甲基磺酸三甲基甲硅烷基酯添加到完全氧化的簇[V 6 O 7 (OMe) 12 ] 2−中，完成了Lindqvist核表面上硅氧化物部分的安装。通过 X 射线光电子能谱对[V 6 O 6 (OSiMe 3 )(OMe) 12 ] 1−的表征表明，硅氧基团的并入不会导致六钒酸盐组件内的电荷分离，这一观察结果与带有替代掺杂剂的团簇的行为。简化的组装[V 6 O 6 (OSiMe 3 )(OMe) 12 ] 2−提供了H掺杂VO 2的等电子模型，其中钒( III )离子嵌入簇核内。值得注意的是，[V 6 O 6 (OSiMe 3 )(OMe) 12 ] 2−的结构分析揭示了硅氧化物官能化钒中心的键扰动，类似于通过从头算计算在 VO 2中吸收 H 原子时引起的键扰动。我们的研究结果提供了对 VO 2中类氢原子掺杂剂安装的局部结构和电子后果的原子精确洞察，并挑战了这些材料中电子-质子共掺杂操作机制的当前观点。
更新日期：2021-09-06
中文翻译：
用多氧钒酸盐簇模拟 VO2 中质子和氢原子吸收的局部结构和电子后果
我们报告了一系列硅氧化物官能化的多氧钒酸盐-醇盐（POV-醇盐）簇的合成和表征，[V 6 O 6 (OSiMe 3 )(OMe) 12 ] n ( n = 1−, 2−)，其用于分别作为二氧化钒中质子和氢原子吸收的分子模型。通过将三氟甲基磺酸三甲基甲硅烷基酯添加到完全氧化的簇[V 6 O 7 (OMe) 12 ] 2−中，完成了Lindqvist核表面上硅氧化物部分的安装。通过 X 射线光电子能谱对[V 6 O 6 (OSiMe 3 )(OMe) 12 ] 1−的表征表明，硅氧基团的并入不会导致六钒酸盐组件内的电荷分离，这一观察结果与带有替代掺杂剂的团簇的行为。简化的组装[V 6 O 6 (OSiMe 3 )(OMe) 12 ] 2−提供了H掺杂VO 2的等电子模型，其中钒( III )离子嵌入簇核内。值得注意的是，[V 6 O 6 (OSiMe 3 )(OMe) 12 ] 2−的结构分析揭示了硅氧化物官能化钒中心的键扰动，类似于通过从头算计算在 VO 2中吸收 H 原子时引起的键扰动。我们的研究结果提供了对 VO 2中类氢原子掺杂剂安装的局部结构和电子后果的原子精确洞察，并挑战了这些材料中电子-质子共掺杂操作机制的当前观点。
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