Related Experiment Video
Updated: Oct 1, 2025
Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Structural Control and Chiroptical Response in Intrinsically Tetra- and Pentanuclear Chiral Gold Clusters
1Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
Abstract:
Controlling the synthesis of chiral metal clusters in the aspects of nuclearity number, metal-metal interaction, and spatial arrangement of metal atoms is crucial for establishing the correlation of detailed structural factors with chiroptical activity. Herein, a series of enantiopure gold complexes with nuclearity numbers ranging from 2 to 5 were constructed and structurally characterized. On the basis of the annulation reaction between two aurated μ2-imido nucleophilic units with various aldehydes, we finely adjusted the metal-metal interaction and torsion angles of a characteristic tetranuclear metal cluster by introducing different substituents into the resulting imidazolidine dianionic chiral skeleton. Further structural investigations, contrast experiments, and time-dependent density functional theory calculations confirmed that the chiroptical response of the acquired asymmetric metal clusters was mainly affected by the geometrically twisted arrangement of metal atoms. Finally, the tetranuclear gold cluster compound with the shortest intermetallic interaction and the largest torsion angle of a Au4 core showed the highest absorption anisotropy factor up to 2.2 × 10-3. In addition, the correlation of structural factors with the stability of chiral gold clusters was thoroughly evaluated by monitoring the CD, UV-vis, and NMR spectra at elevated temperatures. Insight into the relationship between the structural factors with the chiroptical property and stability of chiral gold clusters in this work will help us to design and achieve more stable chiral metal clusters and stimulate their practical applications in chiroptical functional materials.
Related Concept Videos
02:30Chirality at Nitrogen, Phosphorus, and Sulfur
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
02:05Prochirality
02:52Stereoisomerism
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
02:25Molecules with Multiple Chiral Centers
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
02:25Chirality
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...