Probing Conformation Change and Binding Mode of Metal Ion-Carboxyl Coordination Complex through Resonant
Willis Kwun Hei Ho1, Zhi Yong Bao1,2, Xiaorong Gan3,4
1Department of Applied Physics , The Hong Kong Polytechnic University , Hong Kong , China.
Abstract:
Understanding carboxyl-metal ligand interaction has great significance in analytical chemistry. Herein, we use resonant surface-enhanced Raman scattering (SERS) to probe the physiochemical interaction and conformation change in several metal ion-carboxyl coordination complex systems adsorbed on the surface of plasmonically resonant metal nanostructures. Our SERS results and density function theory calculations jointly reveal that low-valence metal ions (such as K+ and Pb2+) tend to bind to the carboxyl active site of a Raman tag molecule, 4-mercaptobenzoic acid (4-MBA), in a unidentate binding mode of low binding energy whereas high-valence metal ions (such as Fe3+) favor a bidentate binding mode of relatively high binding energy. Particularly, Pb2+-ion concentration-dependent SERS suggests a repulsive interaction among the coordination complex leading to a tilted configuration of 4-MBA on the metal surface. This work indicates the resonant SERS approach is suitable not only for studying the carboxyl-metal ligand interaction but also for detecting various types of heavy metal ions at low concentrations.
More Related Videos
Related Concept Videos
03:45Formation of Complex Ions
02:54Coordination Compounds and Nomenclature
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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,...
02:42Valence Bond Theory
02:57Coordination Number and Geometry