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Hydrazone-Based Macrocycles, Fluorop...

Dartmouth College.

Hydrazone-Based Macrocycles, Fluorophores and Light-Activated Switches.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Hydrazone-Based Macrocycles, Fluorophores and Light-Activated Switches.
Author:	Yang, Yin.
Description:	241 p.
Notes:	Source: Dissertation Abstracts International, Volume: 76-07(E), Section: B.
Notes:	Adviser: Ivan Aprahamian.
Contained By:	Dissertation Abstracts International76-07B(E).
Subject:	Organic chemistry.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3685161
ISBN:	9781321607741

Hydrazone-Based Macrocycles, Fluorophores and Light-Activated Switches.
Yang, Yin.

Hydrazone-Based Macrocycles, Fluorophores and Light-Activated Switches. - 241 p.

Source: Dissertation Abstracts International, Volume: 76-07(E), Section: B.

Thesis (Ph.D.)--Dartmouth College, 2015.

This item is not available from ProQuest Dissertations & Theses.

Chapter One: Synthesis of Hydrazone-Based Macrocycles. Macrocyclic molecules with well-defined sizes and shapes are popular synthetic targets used in supramolecular assemblies, host-guest chemistry and molecular recognition. In the past decade, imine-based macrocycles have seen great success in the development of rotaxanes, molecular motors and molecular knots, etc. We hypothesized that hydrazone's unique switching property would make it proper building block of our macrocyclic systems. Several routes have been attempted including symmetric macrocycles from the condensation between hydrazine or hydrazide and aldehyde as well as unsymmetrical hydrazone-based macrocycles with a glycol chain. Promising results indicating the formation of macrocyclic structures 10 and 16 demonstrated the potential and feasibility of this project. Further studies on the metal templation could be conducted to facilitate more selective synthesis and effective purification of our system.

ISBN: 9781321607741Subjects--Topical Terms:

708640
Organic chemistry.

Hydrazone-Based Macrocycles, Fluorophores and Light-Activated Switches.
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245 1 0 $a Hydrazone-Based Macrocycles, Fluorophores and Light-Activated Switches.
300 $a 241 p.
500 $a Source: Dissertation Abstracts International, Volume: 76-07(E), Section: B.
500 $a Adviser: Ivan Aprahamian.
502 $a Thesis (Ph.D.)--Dartmouth College, 2015.
506 $a This item is not available from ProQuest Dissertations & Theses.
520 $a Chapter One: Synthesis of Hydrazone-Based Macrocycles. Macrocyclic molecules with well-defined sizes and shapes are popular synthetic targets used in supramolecular assemblies, host-guest chemistry and molecular recognition. In the past decade, imine-based macrocycles have seen great success in the development of rotaxanes, molecular motors and molecular knots, etc. We hypothesized that hydrazone's unique switching property would make it proper building block of our macrocyclic systems. Several routes have been attempted including symmetric macrocycles from the condensation between hydrazine or hydrazide and aldehyde as well as unsymmetrical hydrazone-based macrocycles with a glycol chain. Promising results indicating the formation of macrocyclic structures 10 and 16 demonstrated the potential and feasibility of this project. Further studies on the metal templation could be conducted to facilitate more selective synthesis and effective purification of our system.
520 $a Chapter Two: BF2-Hydrazone Complexes with Solid-State Emission. The planarity of our hydrazone molecules and their structural resemblance to the dipyromethenes (a precursor of BODIPY systems) led us to develop a family of hydrazone-based solid-state fluorophores upon complexation with a BF2 moiety. Despite their limited emission in solution, our BF2-Hydrazone complexes possess strong fluorescence in the solid-state. Structure-property analysis by comparing a series of BODIHY dyes' X-ray crystallographic data and their photophysical profile has shed light on the emission mechanism of the system. "Rigidification induced emission" (RIE) effect has been proposed to explain the solid-state emission. The planarity, C-H•••pi interaction, pi-pi stacking as well as the molecular arrangement have been found to impact the quantum yield of the fluorophores. In addition, we have demonstrated that the emission profile of BODIHY dyes could be fine-tuned by substituting the parent structure (2) with different electron-donating or -withdrawing groups. The modularity of these derivatives has allowed us to design a solid-state acid/base sensor based on the chromophore core.
520 $a Chapter Three: Visible and Near Infrared Light Switchable BF 2-Coordinated Azo Compounds. Azo compounds have been widely used as photoswitches to control the conformation and activity of biological systems and nanomaterials in a reversible manner. As part of our ongoing investigation into BF2-Hydrazone complex that possesses solid-state fluorescence, we came across a BF2-Azo compound 1 that undergoes a trans/cis isomerization using only visible light. In-depth photoisomerization studies on the photostationary state (PSS), isomerization quantum yield and half-life were conducted using UV-Vis and NMR spectroscopies. Computational studies indicate the reversal of n-pi* and pi-pi* transitions on the energy level upon coordination with the BF2 moiety enables such visible light isomerization to occur. Further effort was made toward red-shifting the activation wavelength of the system as well as the testing of their biocompatibility. We have gained access to a series of near infrared (NIR) light activated BF 2-Azo compounds by substituting various electron-donating amino groups para to the phenyl ring. Photoisomerization analysis proved the high photoconversion and switching efficiency of this series of compounds. Furthermore, the system shows great resistance to biologically reducing conditions ( e.g. glutathione) while relatively short degradation half-life was observed in the aqueous environment.
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