| 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 |
