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Synthesis and properties of new macrocyclic derivates
| dc.contributor.author | Della Sala, Paolo | |
| dc.date.accessioned | 2020-03-18T11:30:38Z | |
| dc.date.available | 2020-03-18T11:30:38Z | |
| dc.date.issued | 2019-02-06 | |
| dc.identifier.uri | http://elea.unisa.it:8080/xmlui/handle/10556/4255 | |
| dc.identifier.uri | http://dx.doi.org/10.14273/unisa-2461 | |
| dc.description | 2017 - 2018 | it_IT |
| dc.description.sponsorship | This PhD thesis is concerned with the design, synthesis and the characterization of new macrocyclic derivatives. Development of new macrocyclic compounds is a particularly interesting because they can involve like building block in Supramolecular chemistry and Nanochemistry. In the first place, I studied the supramolecular properties of different derivatives of the resorcin[6]arenes. Crystal of Resorcin[6]arene was obtained and it reveals that in the solid state the resorcin[6]arene assembles in a twin molecular capsule able to host toluene and ethyl acetate solvent molecules. Subsequently, I have reported the first example of resorcin[6]arene-based cavitand. Sulfate bridges play a double role, both, as structural element for the preorganization of the larger resorcin[6]arene macrocycle and as functional supramolecular interacting groups. Finally, I develop a new multivalent systems resorcin[n]arene based for inhibition of glycosidases and mannosidase that are involved in the malignant transformation of cells. These derivatives were synthetized starting to a pyrrolidine-based iminosugar and resorcinarenes compounds through CuAAS cycloaddition. Biological essays showed that all the resorcinarene derivatives have a good inhibitory activity towards mannosidase enzymes. In second instance, I synthetized new Cycloparaphenylenes (CPP) derivatives to molecular recognition and optoelectronic application. Particularly about molecular recognition field, I reported the synthesis of a [8]CPP derivative incorporating an electron-rich 1,4-dimethoxybenzene ring. This is the first example of substituted CPP derivative reported in literature able to recognize pyridinium guests. Owing to the presence of the 1,4-dimethoxybenzene ring a fine-tuning of the binding abilities toward pyridinium guests was obtained with respect to the native [8]CPP macrocycle. Hybrid Calixarene-CPP derivative that combine the supramolecular features of both the hosts was synthetized and studied in molecular recognition of Na+, Li+ and K+. This derivative shows a noncommon Li+ selectivity due to a more favorable interaction between the cation and the aromatic rings of the CPP bridge. Synthesis of incorporate the 9,10-diphenyl anthracene - [8]CPP derivative was performed and were studied optical and electronical features to obtain the first example of a CPP-based emitter in photon upconversion in the presence of the of octaethylporphyrin Pd(II) complex as a sensitizer, thus widening the application fields of this class of compounds. Finally, [8]CPP and [10]CPP was tested to produce Luminescent Solar Concentrators (LSCs). The high Stokes shift of the CPP macrocycles, enables the preparation of slabs in which a low reabsorption was observed. The results here obtained show clearly the photophysical performances of the CPPbased LSC closely matches with that of the lanthanide chelates based LSC, of interest for applications in colorless LSC. [edited by Author] | it_IT |
| dc.language.iso | en | it_IT |
| dc.publisher | Universita degli studi di Salerno | it_IT |
| dc.subject | Macrocycles | it_IT |
| dc.subject | Cycloparaphenylenes | it_IT |
| dc.subject | Molecular recognitions | it_IT |
| dc.title | Synthesis and properties of new macrocyclic derivates | it_IT |
| dc.type | Doctoral Thesis | it_IT |
| dc.subject.miur | CHIM/06 CHIMICA ORGANICA | it_IT |
| dc.contributor.coordinatore | Guerra, Gaetano | it_IT |
| dc.description.ciclo | XXXI ciclo | it_IT |
| dc.contributor.tutor | Gaeta, Carmine | it_IT |
| dc.identifier.Dipartimento | Chimica e Biologia "A. Zambelli" | it_IT |
