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^(31)P NMR Studies on the ligand dissociation of Trinuclear Molybdenum Cluster Compounds

Chinese Journal of Chemistry 2003年第9期21卷 1174-1177页

作者：李兆基覃业燕唐艳红康遥夏继波陈忠吴棱姚元根 State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou Fujian 350002 China Department of Chemistry Xiamen University Xiamen Fujian 361005 China

A series of carboxylate-substituted trinuclear molybdenum cluster compounds formulated as Mo 3S 4(DTP) 3(RCO 2)(L), where R=H, CH 3, C 2H 5, CH 2Cl, CCl 3, R 1C 6H 4 (R 1 is the group on the benzene ring of aromatic carboxylate), L=pyridine, CH 3CN, DMF, have been synthesized by the ligand substitution reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by 31P NMR. The dissociation process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution structure and reactive properties of the cluster. The long-distance interaction between ligands RCO 2 and L is transported by Mo 3S 4 core.

关键词： 31P NMR molybdenum cluster ligand dissociation

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Turning weak into strong: on the CTAB-induced active surface growth

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Science China Chemistry 2022年第7期65卷 1299-1305页

作者： Yonglong Zheng Jianpeng Zong Ting Xiang Quan Ren Dongmeng Su Yuhua Feng Yawen Wang Hongyu Chen Institute of Advanced Synthesis(IAS) School of Chemistry and Molecular EngineeringJiangsu National Synergetic Innovation Centre for Advanced MaterialsNanjing Tech UniversityNanjing 211816China School of Science Westlake UniversityHangzhou 310023China

Discovering new methods and principles in the inequivalent growth of equivalent facets is of great significance for going beyond symmetrical nanocrystals and for out-of-box exploration. In this work, we demonstrate that a middle ground exists between the traditional weak ligands and the strong ligands with unusual growth modes. By modifying the seed concentration during the growth of pentagonal Au nanorods, the typical weak ligand cetyltrimethylammonium bromide(CTAB) is made strong, leading to notches of restricted growth and even the active surface growth mode. In-depth investigation in the link between growth kinetics and ligand packing reveals the principle of their interplay —— that the on-off dynamics of the ligands only allows for a certain limit of materials deposition rate. Beyond this limit, the growth materials build up and are then diverted elsewhere, leading to inequivalent growth. The fact that a freshly grown surface has few ligands promotes the active surface growth, focusing the growth materials onto a few sites. We believe that the knowhow of interfering ligand packing via growth kinetics would offer a powerful tool of synthetic control, where the facet-and curvature-dependent ligand packing is expected to be useful synthetic handles.

关键词： facet control ligand packing active surface growth Au deposition ligand dissociation

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