Synthesis And Properties Of Fused Nickel (?) Norcorrole Derivatives

Norcorrolatonickel(?)has been studied by more and more researchers because of its reversible redox properties,unique reactivity and potential applications in rechargeable batteries,electrochemical sensors,and electrically active materials.In this paper,we focus on the properties of the exocyclic double bond of norcorrolatonickel(?),studying its cyclization or cycloaddition reaction.At the same time,the spectrum,electrochemical and magnetic ring current properties of the obtained fused compounds are studied.and some effective results was obtained:In the first chapter,the discovery of norcorrolatonickel(?)and the synthesis of various kinds of norcorrole are described.Afterwards,the nature of norcorrolatonickel(?)was briefly described.The reactivity of this reaction focuses on the derivatization of norcorrolatonickel(?),including the insertion reaction,nucleophilic substitution reaction,reduction reaction and electrophilic substitution reaction.In the second chapter,At room temperature,norcorrolatonickel(?)reacts with isoamylnitrite by controlling the reaction reagents and reaction temperature to selectively nitrify to give mononitro norcorrolatonickel(?),which is then reduced with tin chlorideto give monoaminated norcorrolatonickel(?).Then,in the absence of catalyst,monoaminated norcorrolatonickel(?)with variously substituted aryl aldehydes in refluxing toluene under anaerobic conditionsand to form a series of dimers.Remarkably,treatment of dimers with pchloranil induced a Hantzsch-like oxidative cyclization to produce pyridine-Fused Bis(Norcorrole)dimers comprising two antiaromatic macrocycles communicating by an aromatic moiety.The spectrum,electrochemical and magnetic ring current properties of the compound were studied.all of which revealed unexpected antiaromaticity enhancement in the fused system.In the third chapter,The antiaromatic ring of norcorrole,a contracted tetrapyrrolic porphyrinoid,was subjected to [2+3] dipolar cycloaddition of iminonitriles.The paratropic character of the resulting chiral chlorines was retained.The chlorins were easily dehydrogenated in the presence of air,yielding pyrazole-fused norcorroles.The cycloaddition reaction of mononitro norcorrolatonickel(?)with bromoanthraquinones resulted in the direct synthesis of four new pyrazole-fused mononitro norcorrolatonickel(?).The obtained compounds were characterized by high resolution mass spectrometry,one-dimensional and two-dimensional nuclear magnetic resonance spectroscopy,and UV/Vis/NIR spectra.Some of the compounds were also confirmed by single crystal X-ray diffraction.The magnetic properties of the chiral product were determined by nucleus independent chemical shift(NICS)values,and it was found that the paratropic ring current of pyrazole-fused norcorroles formed after the oxidative dehydrogenation were enhanced,and the reactivity of the compound was also significantly enhanced.At the same time,the spectral and electrochemical properties of pyrazole-fused norcorroles were studied.