Related Experiment Video
Updated: May 28, 2026
Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Quantum chemical study of redox-switchable second-order nonlinear optical responses of D-π-A system BNbpy and metal
Na-Na Ma1, Shi-Ling Sun, Chun-Guang Liu
1Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, People's Republic of China.
Abstract:
A second-order nonlinear optical (NLO) molecular switching with redox has been investigated in the present paper. The static first hyperpolarizabilities of 5-(BMes(2))-5'-(NPh(2))-2,2'-bipyridine (BNbpy) containing three-coordinate organoboron, Pt(II) chelate complex Pt(BNbpy)Ph(2), and their reduced forms have been calculated by density functional theory (DFT) combined with the analytic derivatives method. There is an enhancement of static first hyperpolarizabilities in the reduced form according to the calculations. That is, the β(vec) value of one-electron-reduced form is ~7 times as large as that of neutral form BNbpy; the β(vec) values of one- and two-electron-reduced forms are ~3 and ~4 times as large as that of neutral form Pt(BNbpy)Ph(2), respectively. In particular, the β(vec) value of two-electron-reduced form (3)Pt(BNbpy)Ph(2)(2-) is 1349 × 10(-30) esu, ~286 times larger than its neutral form. Moreover, the component β(z) value of the metal chelate complex Pt(BNbpy)Ph(2) is 25 × 10(-30) esu, which is ~14 times as large as that of ligand BNbpy; the corresponding F(-)/CN(-) compounds show a decrease in β(x) values compared with the case of the ligand and Pt(II) complex. Analyses of geometries, density of states (DOS), and time-dependent DFT (TDDFT) calculations reveal that the one-electron reduction promotes the molecular conjugation in the x-axis and intensifies the interaction between the metal Pt(II) and ligand and then results in an enhancement of the static first hyperpolarizability, whereas the binding of F(-)/CN(-) to the B atom turns off the p(π)-π* conjugation and has no effect on the conjugation of bipyridine, which leads to a decreasing β value in the x-axis.
More Related Videos
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
11:38Quantifying the Binding Interactions Between Cu(II) and Peptide Residues in the Presence and Absence of Chromophores
Published on: April 5, 2022
Related Concept Videos
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
02:42Valence Bond Theory
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...
01:19Complexation Equilibria: The Chelate Effect
02:51Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
01:27π Electron Effects on Chemical Shift: Overview