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2014 | Buch

Photofunctionalization of Molecular Switch Based on Pyrimidine Ring Rotation in Copper Complexes

verfasst von: Michihiro Nishikawa

Verlag: Springer Japan

Buchreihe : Springer Theses

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Über dieses Buch

This book provides a detailed description of photofunctionalization of molecular switch based on pyrimidine ring rotational isomerization in copper complexes bearing two bidentate ligands. The most important features of this work focus on the properties associated with the rotational isomerization based on the two possible coordination geometries at the copper center derived from two nitrogen atoms on the unsymmetrically substituted pyrimidine ring. The functions of systems such as dual emission and redox potential switching based on photo-driven rotation will be of particular interest to readers. Both the functions and the procedures for proving these phenomena are beneficial for the development of more functionalized systems based on material science, molecular science, nanoscience, nanotechnology, electrochemistry, photochemistry, coordination chemistry, physical chemistry, and related disciplines. The finding elucidated here holds promise for handling the photoprocesses of metal complexes, valid for both applications and novel properties. This system is expected make it possible to extract an electrochemical potential response from molecular switches, aiming to simulate the five senses of human beings at a single molecular level.

Inhaltsverzeichnis

Frontmatter
Chapter 1. General Introduction
Abstract
I described general introduction for importance of metal complexes, well-established unique nature of copper complexes bearing diimines, and the previous research of our group on stimuli-responsive pyrimidine ring rotation in copper complexes. An advantage of our system is that we can extract useful electric responses from a simple multistable molecule. The aim of studies in my Ph.D course on development of new types of emission and photoresponsivity by photofunctionalization of the copper complex system is described.
Michihiro Nishikawa
Chapter 2. Details of Molecular Bistability Based on Pyrimidine Ring Rotation in Copper(I) Complexes
Abstract
The rational molecular design requires a detailed investigation for the equilibrium between two rotational isomers derived from orientation of pyrimidine ring. I studied on chemistry of rotational equilibrium in newly synthesized copper(I) complexes bearing two bidentate ligands, pyridylpyrimidine and bulky diphosphine, using 1H NMR and single crystal X-ray structural analysis. I found that ion-pairing sensitivities of rotational bistability in the view point of both thermodynamics and kinetics, evidence for intramolecular process of interconversion, and suitability of common organic solution state for the desired function.
Michihiro Nishikawa
Chapter 3. Dual Emission Caused by Ring Rotational Isomerization of a Copper(I) Complex
Abstract
Photophysics of metal complexes is valid for photofunctional devices. Transient emission spectra measurement is a powerful way to find difference in photoprocesses between two rotational isomers which interconvert and coexist in the solution. I developed a molecular system which exhibited heat-sensitive dual luminescence behavior caused by the pyrimidine ring rotational isomerization in copper(I) complexes. This finding is valuable for the novel way to handle the photoprocesses of transition metal complexes.
Michihiro Nishikawa
Chapter 4. Repeatable Copper(II)/(I) Redox Potential Switching Driven Visible Light-Induced Coordinated Ring Rotation
Abstract
Repeatable PET-driven rotational isomerization is described. I demonstrated the conversion of light stimuli into electrochemical potential via reversibly working artificial molecular rotation, using two strategies, DMFc+ system and partial oxidation system. In both systems, photoinduced electron transfer from copper complex to electron acceptor plays a key role for the photo- and heat-driven rotation.
Michihiro Nishikawa
Chapter 5. Concluding Remarks
Abstract
As I described in Chap.​ 1, metal complexes bearing π-conjugated chelating ligands are valid for both application and novel properties (Sect.​ 1.​1). Their unique photophysics, derived from a formation of long-lived charge transfer excited state, is of much interest for dye-sensitized solar cell, light-emitting devices, and photocatalyst. Reversible redox activities of metal complexes are useful in nanotechnology applications such as in molecular electronics, photoelectronic functions, and molecular machines, where the function of muscle is well-imitated at the molecular level.
Michihiro Nishikawa
Backmatter
Metadaten
Titel
Photofunctionalization of Molecular Switch Based on Pyrimidine Ring Rotation in Copper Complexes
verfasst von
Michihiro Nishikawa
Copyright-Jahr
2014
Verlag
Springer Japan
Electronic ISBN
978-4-431-54625-2
Print ISBN
978-4-431-54624-5
DOI
https://doi.org/10.1007/978-4-431-54625-2

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