Preparation And Properties Of Gels Based On TYF-Amide Derivatives

Because of their unique electron–donating and redox properties, tetrathiafulvalene(TTF) and its derivatives have attracted great interest for a long time and have been widelyused in energy material, molecular device and supramolecular chemistry. The amidegroups can form rich hydrogen–bonds, which make them have good application inmolecular assembling and responding. Organic low molecular weight gelators withtetrathiafulvalene (TTF) unit have received considerable attention because the formed gelsusually exhibit redox active response and conducting or semiconducting properties.However, metal coordination systems have not been reported for TTF–derived gels up todate.In this thesis, we pay attention to the study on a series of TTF derivatives with adiamide–diamino moiety. The major contents we researched are as follows:In introduction, the properties and important achievements of TTF derivatives arereviewed briefly. Recent researches on TTF–amide and dioxotetraamine (diamino–diimido)ligands are summarized. Especially, the new researches on molecular recognition of thesecompounds are described.Besides, TTF based organogels containing amide moiety are alsoreviewed.In chapter2, we newly designed and synthesized a series of redox active TTFderivatives (TTF–(CONHCH2CH2NH–CnH2n+1)2(L1n=4, L2n=8, L3n=12) with adiamide–diamino moiety that can selectively coordinate to specific metal ions with squarecoordination geometry. Gelation properties and morphologies of the films prepared by thegelators in different hydrophobic solvents are characterized. The TTF derivative withdodecyl group shows effective gelation property and electrodes with the organogel filmsare prepared. The effect of the Ni(II) and Cu(II) coordination on the photocurrent response property of the electrodes is examined. The metal square coordination significantlyincreases the photocurrent response. This gel system is the first metal coordination relatedTTF–gel based photoelectric material. The mechanism of metal coordination–improvedphotocurrent response property is discussed based on the crystal structural analysis andtheoretical calculations.In chapter3, the gel containing chloranil can also be successfully prepared. Scanningelectron microscope (SEM) and atomic force microscope (AFM) studies show that thexerogels exhibit rope–like frameworks. Both absorption and electron spin resonance (ESR)spectroscopic investigations reveal that the TTF unit is oxidized into TTF+bychloranil.The Redox responsive gels can be transferred between sol and gel states by I2and TCNQs (7,7,8,8–tetracyanoquinodimethane). Finally, the electrochemical propertiesand the photocurrent response of the gel containing chloranil were also investigated.In chapter4, we synthesized a redox active TTF derivative, TTF–(CONHCH2CH2–NHCnH2n+1)2(L4n=1). Supramolecular compounds of protonated [H2L4]+with SO42–,C2O42–and NO3–anions were synthesized. The crystal structures of the complexes weredetermined by single crystal X–ray diffraction. As the model compounds, The effect ofanions and cations on the redox recognitions and photocurrent response property of theoxidation–gel to will be investigated.