Mauriello, Francesco
(2008)
Optically active photoresponsive multifunctional polymeric materials, [Dissertation thesis], Alma Mater Studiorum Università di Bologna.
Dottorato di ricerca in
Chimica industriale, 20 Ciclo. DOI 10.6092/unibo/amsdottorato/711.
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Abstract
In the last year [1], Angiolini and co-workers have synthesized and investigated
methacrylic polymers bearing in the side chain the chiral cyclic (S)-3-hydroxypyrrolidine
moiety interposed between the main chain and the trans-azoaromatic chromophore,
substituted or not in the 4’ position by an electron-withdrawing group. In these materials, the
presence of a rigid chiral moiety of one prevailing absolute configuration favours the
establishment of a chiral conformation of one prevailing helical handedness, at least within
chain segments of the macromolecules, which can be observed by circular dichroism (CD).
The simultaneous presence of the azoaromatic and chiral functionalities allows the polymers
to display both the properties typical of dissymmetric systems (optical activity, exciton
splitting of dichroic absorptions), as well as the features typical of photochromic materials
(photorefractivity, photoresponsiveness, NLO properties).
The first part of this research was to synthesize analogue homopolymers and copolymers
based on bisazoaromatic moiety and compare their properties to those of the above mentioned
analogue derivatives bearing only one azoaromatic chromophore in the side chain. We
focused also the attention on the effects induced on the thermal and chiroptical behaviours by
the insertion of particulars achiral comonomers characterized by different side-chain mobility
and grown hindrance (MMA, tert-BMA and TrMA).
On the other hand carbazole containing polymers [2] have attracted much attention
because of their unique features. The use of these materials in advanced micro- and
nanotechnologies spreads in many different applications such as photoconductive and
photorefractive polymers, electroluminescent devices, programmable optical
interconnections, data storage, chemical photoreceptors, NLO, surface relief gratings, blue
emitting materials and holographic memory.
The second part of the work was focused on the synthesis and the characterization polymeric
derivatives bearing in the side chain carbazole or phenylcarbazole moieties linked to the (S)-
2-hydroxy succinimide or the (S)-3-hydroxy pyrrolidinyl ring as chiral groups covalently
linked to the main chain through ester bonds.
The last objective of this research was to design, synthesize, and characterize multifunctional
methacrylic homopolymers and copolymers bearing three distinct functional groups (i.e.
azoaromatic, carbazole and chiral group of one single configuration) directly linked in the
side chain.
This polymeric derivatives could be of potential interest for several advanced application
fields, such as optical storage, waveguides, chiroptical switches, chemical photoreceptors,
NLO, surface relief gratings, photoconductive materials, etc.
Abstract
In the last year [1], Angiolini and co-workers have synthesized and investigated
methacrylic polymers bearing in the side chain the chiral cyclic (S)-3-hydroxypyrrolidine
moiety interposed between the main chain and the trans-azoaromatic chromophore,
substituted or not in the 4’ position by an electron-withdrawing group. In these materials, the
presence of a rigid chiral moiety of one prevailing absolute configuration favours the
establishment of a chiral conformation of one prevailing helical handedness, at least within
chain segments of the macromolecules, which can be observed by circular dichroism (CD).
The simultaneous presence of the azoaromatic and chiral functionalities allows the polymers
to display both the properties typical of dissymmetric systems (optical activity, exciton
splitting of dichroic absorptions), as well as the features typical of photochromic materials
(photorefractivity, photoresponsiveness, NLO properties).
The first part of this research was to synthesize analogue homopolymers and copolymers
based on bisazoaromatic moiety and compare their properties to those of the above mentioned
analogue derivatives bearing only one azoaromatic chromophore in the side chain. We
focused also the attention on the effects induced on the thermal and chiroptical behaviours by
the insertion of particulars achiral comonomers characterized by different side-chain mobility
and grown hindrance (MMA, tert-BMA and TrMA).
On the other hand carbazole containing polymers [2] have attracted much attention
because of their unique features. The use of these materials in advanced micro- and
nanotechnologies spreads in many different applications such as photoconductive and
photorefractive polymers, electroluminescent devices, programmable optical
interconnections, data storage, chemical photoreceptors, NLO, surface relief gratings, blue
emitting materials and holographic memory.
The second part of the work was focused on the synthesis and the characterization polymeric
derivatives bearing in the side chain carbazole or phenylcarbazole moieties linked to the (S)-
2-hydroxy succinimide or the (S)-3-hydroxy pyrrolidinyl ring as chiral groups covalently
linked to the main chain through ester bonds.
The last objective of this research was to design, synthesize, and characterize multifunctional
methacrylic homopolymers and copolymers bearing three distinct functional groups (i.e.
azoaromatic, carbazole and chiral group of one single configuration) directly linked in the
side chain.
This polymeric derivatives could be of potential interest for several advanced application
fields, such as optical storage, waveguides, chiroptical switches, chemical photoreceptors,
NLO, surface relief gratings, photoconductive materials, etc.
Tipologia del documento
Tesi di dottorato
Autore
Mauriello, Francesco
Supervisore
Co-supervisore
Dottorato di ricerca
Ciclo
20
Coordinatore
Settore disciplinare
Settore concorsuale
Parole chiave
materiali polimerici multifunzionali amplificazione chiralità polimeri fotocromici otticamente attivi polimeri fotorifrattivi
URN:NBN
DOI
10.6092/unibo/amsdottorato/711
Data di discussione
20 Maggio 2008
URI
Altri metadati
Tipologia del documento
Tesi di dottorato
Autore
Mauriello, Francesco
Supervisore
Co-supervisore
Dottorato di ricerca
Ciclo
20
Coordinatore
Settore disciplinare
Settore concorsuale
Parole chiave
materiali polimerici multifunzionali amplificazione chiralità polimeri fotocromici otticamente attivi polimeri fotorifrattivi
URN:NBN
DOI
10.6092/unibo/amsdottorato/711
Data di discussione
20 Maggio 2008
URI
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