From f0f3516025b182e8fbbd597c036d02e5c55fb073 Mon Sep 17 00:00:00 2001 From: Davide Grilli Date: Thu, 15 Oct 2026 13:58:09 +0200 Subject: [PATCH] Aggiunge cartella presentazione con regole, discorso, slide Marp e immagini Co-Authored-By: Claude Sonnet 5.5 --- presentazione/discorso.md | 158 ++++++++++ .../images/fig-film-copolimeri-uv.jpg | Bin 0 -> 64701 bytes .../images/fig-sistemi-fluorofori.png | Bin 0 -> 183435 bytes presentazione/images/fig-uv-dpp1.jpg | Bin 0 -> 61337 bytes presentazione/images/fig-uv-dpp2.jpg | Bin 0 -> 54903 bytes presentazione/images/fig1-dpp.jpg | Bin 0 -> 13200 bytes presentazione/images/fig2-sintesi-dpp1.jpg | Bin 0 -> 21393 bytes .../images/fig3-alchilazione-dpp2.jpg | Bin 0 -> 21403 bytes .../images/fig4-copolimerizzazione.jpg | Bin 0 -> 23421 bytes .../images/fig5-rop-bottle-brush.jpg | Bin 0 -> 32846 bytes presentazione/images/fig6-uv-em-3.2b.jpg | Bin 0 -> 52818 bytes presentazione/images/fig7-bandgap-vs-dpp.jpg | Bin 0 -> 31109 bytes presentazione/regole.md | 17 ++ presentazione/slides.md | 274 ++++++++++++++++++ 14 files changed, 449 insertions(+) create mode 100644 presentazione/discorso.md create mode 100644 presentazione/images/fig-film-copolimeri-uv.jpg create mode 100644 presentazione/images/fig-sistemi-fluorofori.png create mode 100644 presentazione/images/fig-uv-dpp1.jpg create mode 100644 presentazione/images/fig-uv-dpp2.jpg create mode 100644 presentazione/images/fig1-dpp.jpg create mode 100644 presentazione/images/fig2-sintesi-dpp1.jpg create mode 100644 presentazione/images/fig3-alchilazione-dpp2.jpg create mode 100644 presentazione/images/fig4-copolimerizzazione.jpg create mode 100644 presentazione/images/fig5-rop-bottle-brush.jpg create mode 100644 presentazione/images/fig6-uv-em-3.2b.jpg create mode 100644 presentazione/images/fig7-bandgap-vs-dpp.jpg create mode 100644 presentazione/regole.md create mode 100644 presentazione/slides.md diff --git a/presentazione/discorso.md b/presentazione/discorso.md new file mode 100644 index 0000000..f0023f1 --- /dev/null +++ b/presentazione/discorso.md @@ -0,0 +1,158 @@ +# Discorso della presentazione + +Testo da pronunciare per la presentazione di 14 diapositive (titolo, 12 di contenuto, ringraziamenti; più 3 di scorta in fondo), pensato per **12 minuti** (limite: 12 ± 1 min) a un ritmo di circa 135 parole al minuto. Il segno **▶ CAMBIA SLIDE** indica quando passare alla diapositiva successiva. Per ogni slide sono indicati il tempo previsto e il tempo cumulativo a cui dovresti trovarti all'inizio. + +## Tabella dei tempi + +| # | Slide | Durata | Inizio | +|---|---|---|---| +| 1 | Titolo | 0:20 | 0:00 | +| 2 | Soft optoelectronics | 0:55 | 0:20 | +| 3 | ACQ | 0:50 | 1:15 | +| 4 | DPP | 0:55 | 2:05 | +| 5 | Sistemi polimerici emissivi | 0:55 | 3:00 | +| 6 | Strategia bottle brush | 0:55 | 3:55 | +| 7 | Sintesi del monomero | 1:00 | 4:50 | +| 8 | Copolimerizzazione ossidativa | 1:05 | 5:50 | +| 9 | Copolimeri lineari spenti | 0:50 | 6:55 | +| 10 | ROP: bottle brush | 1:05 | 7:45 | +| 11 | Proprietà ottiche | 1:15 | 8:50 | +| 12 | Proprietà elettrochimiche | 1:10 | 10:05 | +| 13 | Conclusioni | 0:50 | 11:15 | +| 14 | Ringraziamenti | 0:10 | 12:05 | + +Se a metà (slide 8) sei oltre 6:15, taglia le frasi tra parentesi quadre: sono pensate per essere saltabili. + +--- + +## Slide 1 · Titolo (0:00 – 0:20) + +Buongiorno a tutti, sono Aurora Luzi e presento la mia tesi magistrale, dal titolo «Sintesi e caratterizzazione di copolimeri bottle brush foto-elettro attivi». Il lavoro è stato svolto con il relatore, il dottor Stefano Scurti, e con i correlatori, il professor Massimiliano Lanzi, il dottor Simone Gabellini e il dottor Riccardo Medri. + +**▶ CAMBIA SLIDE** + +## Slide 2 · Soft optoelectronics (0:20 – 1:15) + +Il lavoro si inserisce nella soft optoelectronics, il ramo che combina emissione e rilevamento della luce con dispositivi flessibili e adattabili. I semiconduttori organici con estesi sistemi π-coniugati sono leggeri e flessibili, e si depositano da soluzione a basse temperature, con una riduzione dei costi e dell'impatto ambientale rispetto ai semiconduttori inorganici rigidi come il silicio. + +Possono convertire segnali elettrici in fotoni, come negli OLED, i diodi organici a emissione di luce, oppure fare il contrario, come nelle celle fotovoltaiche. Per usarli in un dispositivo, però, bisogna governarne le proprietà ottiche ed elettroniche, cioè ingegnerizzare il band gap. + +La strategia d'elezione è l'approccio donatore-accettore: si alternano lungo lo scheletro unità elettron-ricche e unità elettron-deficienti, e il trasferimento di carica intramolecolare che ne deriva riduce il salto energetico e porta assorbimento ed emissione nel visibile. + +**▶ CAMBIA SLIDE** + +## Slide 3 · ACQ (1:15 – 2:05) + +Questi materiali hanno però un limite importante: spesso perdono le proprietà ottiche allo stato solido. Lo scheletro è altamente planare, quindi le catene vicine tendono a impilarsi, il cosiddetto π-stacking. + +In soluzione le catene sono isolate dal solvente e il materiale emette. Allo stato solido, invece, l'energia dell'eccitone viene dissipata in modo non radiativo e la fluorescenza si smorza. Questo fenomeno si chiama Aggregation-Caused Quenching, in sigla ACQ. + +Il problema è concreto: nello strato emissivo di un OLED serve proprio l'emissione, quindi l'ACQ ne limita le applicazioni pratiche. + +**▶ CAMBIA SLIDE** + +## Slide 4 · DPP (2:05 – 3:00) + +Come unità accettrice abbiamo scelto il dichetopirrolopirrolo, il DPP, in figura. Il suo nucleo è planare, rigido e fortemente elettron-deficiente. L'elevata coniugazione e i legami a idrogeno tra le unità lattamiche danno una grande stabilità termica, ma anche una scarsa solubilità nei comuni solventi organici. + +Il DPP è però molto versatile. I protoni ammidici si possono deprotonare con basi forti, e l'N-alchilazione elimina i legami a idrogeno e aumenta la solubilità: un semplice metile la accresce di 27 volte in DMF. I sostituenti tiofenici in posizione 3 e 6 sono invece i siti per bromurazione e cross-coupling, e per la polimerizzazione dello scheletro. + +**▶ CAMBIA SLIDE** + +## Slide 5 · Sistemi polimerici emissivi (3:00 – 3:55) + +Resta da decidere come legare il fluoroforo alla matrice polimerica, e questa scelta influenza drasticamente le proprietà finali. Nei sistemi host-guest, il caso a, il fluoroforo è disperso nella matrice: è semplice, ma l'ospite migra e aggrega, e la resa quantica cala. Nei sistemi cross-linked, il caso d, il cromoforo è ancorato da ponti chimici, ma il materiale diventa fragile e insolubile. + +Restano i sistemi side-chain, caso c, e main-chain, caso b, in cui il fluoroforo è legato covalentemente. Una strategia riuscita è il grafting-from: un DPP con due gruppi ossidrilici inizia la crescita di due catene di policaprolattone, il PCL, per polimerizzazione ad apertura di anello, dando PCL-DPP-PCL. Noi abbiamo esteso questa idea a uno scheletro semiconduttore DPP-3HT, dove 3HT è il 3-esiltiofene. + +**▶ CAMBIA SLIDE** + +## Slide 6 · Strategia bottle brush (3:55 – 4:50) + +Ecco quindi la domanda di ricerca: un'architettura bottle brush, cioè a spazzola, può superare l'ACQ allo stato solido mantenendo l'integrità elettrochimica del core DPP? L'idea è che le catene laterali separino fisicamente i segmenti planari coniugati. + +Il lavoro si articola in quattro fasi: la sintesi di un monomero ortogonale derivato dal DPP; la copolimerizzazione ossidativa con 3HT per ottenere lo scheletro; l'innesto delle catene laterali di PCL per ROP dell'ε-caprolattone; e infine la caratterizzazione dei materiali. + +Il monomero è ortogonale perché porta due gruppi con ruoli indipendenti: i tiofeni fanno crescere lo scheletro con il cloruro ferrico, mentre i due ossidrili sono gli iniziatori della ROP e daranno le catene di PCL. + +**▶ CAMBIA SLIDE** + +## Slide 7 · Sintesi del monomero (4:50 – 5:50) + +Prima fase: la sintesi del monomero. Il DPP tiofenico **1** si ottiene per ciclizzazione pseudo-Stobbe tra 2-cianotiofene e diisopropil succinato. Il succinato è aggiunto lentamente, e si è scelto quello diisopropilico, più ingombrato, per ridurre l'autocondensazione di Claisen. Il prodotto è un solido rosso scuro violaceo, con assorbimento a 531 nm ed emissione a 542 nm in THF. + +Poi l'N-alchilazione con 6-bromo-1-esanolo, in DMSO con ter-butossido di potassio, dà il monomero **2**, con due braccia idrossiesiliche. L'avvenuta alchilazione è confermata dal ¹H-NMR, con i multipletti a 4,1 e 3,6 ppm, e dal FT-IR, con la banda dell'O-H a circa 3400 cm⁻¹. + +**▶ CAMBIA SLIDE** + +## Slide 8 · Copolimerizzazione ossidativa (5:50 – 6:55) + +Seconda fase: il monomero **2** viene copolimerizzato con il 3HT per via ossidativa, con cloruro ferrico in nitrometano e cloroformio anidro. Abbiamo scelto il cloruro ferrico perché non richiede la pre-funzionalizzazione dei monomeri e lavora a temperatura e pressione ambiente, a fronte di un minor controllo su polidispersità e regioregolarità. [L'ossidante è stato rimosso con lavaggi acidi, perché tracce di metalli di transizione spegnerebbero la fluorescenza.] + +Abbiamo alimentato il 20, il 50 e l'80% in moli di DPP, ma, come mostra la tabella, la percentuale reale, determinata via ¹H-NMR, non supera il 35%: il tiofene, più reattivo e meno voluminoso, addiziona preferenzialmente rispetto al DPP, ingombrante. Le masse molecolari medie in numero sono tra 1402 e 2149 dalton, e i valori di PD intorno a 2 o superiori sono attesi per una polimerizzazione non controllata. + +**▶ CAMBIA SLIDE** + +## Slide 9 · Copolimeri lineari spenti (6:55 – 7:45) + +Come si comportano questi copolimeri? In soluzione di THF i tre hanno profili ottici pressoché identici a quello del monomero, con assorbimento tra 540 e 544 nm ed emissione intorno a 550 nm. + +Allo stato solido, però, il comportamento cambia drasticamente. Come si vede dai film sotto lampada UV, non c'è emissione apprezzabile: l'intenso impaccamento delle catene forma aggregati che disattivano i fluorofori. L'ACQ è quindi confermata. [La DSC mostra una transizione vetrosa intorno a −10 °C e nessuna fusione, a conferma della natura random dei copolimeri.] Questo giustifica il passaggio al design bottle brush. + +**▶ CAMBIA SLIDE** + +## Slide 10 · ROP: i bottle brush (7:45 – 8:50) + +Terza fase: dagli ossidrili di **3b** e **3c** abbiamo fatto crescere le catene di PCL per ROP dell'ε-caprolattone, in toluene a 110 °C con stagno ottanoato come catalizzatore. Dosando il monomero sul numero di ossidrili, abbiamo ottenuto catene laterali nominali di 1500, 5000 e 10000 dalton, per un totale di sei bottle brush. Il copolimero **3a** non è stato usato per la scarsa efficienza della sua via sintetica. + +L'innesto è confermato dal ¹H-NMR, con il tripletto del PCL a circa 4,0 ppm, e dal FT-IR: scompare la banda dell'O-H e compare il C=O estereo a circa 1720 cm⁻¹. + +Le masse molecolari da GPC, in tabella, sono significativamente sottostimate rispetto ai valori teorici: la GPC separa per volume idrodinamico, e un polimero molto ramificato è compatto in soluzione. Questo conferma indirettamente la struttura ramificata e altamente impaccata. L'unica eccezione è **3.3c**, che si discosta dall'andamento. + +**▶ CAMBIA SLIDE** + +## Slide 11 · Proprietà ottiche (8:50 – 10:05) + +Veniamo alla caratterizzazione ottica. In soluzione di THF tutti i bottle brush hanno assorbimento tra 544 e 554 nm, emissione tra 557 e 564 nm e Stokes shift tra 8 e 14 nm. Quindi la funzionalizzazione sterica non perturba l'integrità elettronica del core DPP, e il basso Stokes shift conferma che il cromoforo resta planare. + +Poi il passaggio decisivo: lo stato solido, studiato sul campione **3.2b**. Nel grafico la linea continua è la soluzione e quella tratteggiata il solido; in nero l'assorbimento, in rosso l'emissione. Allo stato solido l'assorbimento si sposta verso il rosso, a 570-580 nm, per la planarizzazione dello scheletro. L'emissione si allarga e si sposta a 650-660 nm, con uno Stokes shift di circa 80-90 nm: è il segno di una forte aggregazione, con stati di tipo H e J secondo il modello di Kasha. + +Nonostante questi riarrangiamenti, però, il bottle brush mantiene un'apprezzabile emissione nel rosso. Le catene di PCL agiscono da spaziatore sterico e attenuano i percorsi di disattivazione non radiativa tipici dell'ACQ. + +**▶ CAMBIA SLIDE** + +## Slide 12 · Proprietà elettrochimiche (10:05 – 11:15) + +Resta da verificare che il design bottle brush non comprometta le proprietà elettroniche, da cui dipende il comportamento da semiconduttore. Con la ciclovoltammetria, calibrata sul ferrocene, abbiamo ricavato HOMO, LUMO e band gap elettrochimico. + +Nei copolimeri lineari il band gap cresce da 0,970 a 1,371 elettronvolt all'aumentare della frazione reale di DPP, da 25,2 a 35,3%, con andamento lineare, come si vede nel grafico. Il DPP riduce la lunghezza di coniugazione effettiva e stabilizza il LUMO, favorendo l'iniezione di elettroni: la composizione monomerica diventa quindi un parametro di controllo del band gap. + +Nei bottle brush il band gap è compreso tra 0,929 e 1,521 elettronvolt. I processi redox avvengono sul core DPP-3HT, mentre i rami alifatici fungono da matrice dielettrica: l'elettroattività dello scheletro è conservata. + +**▶ CAMBIA SLIDE** + +## Slide 13 · Conclusioni (11:15 – 12:05) + +Per concludere. Abbiamo ottenuto tre copolimeri statistici e due serie di bottle brush con catene di PCL di lunghezza nominale crescente. Il design proposto combina proprietà elettrochimiche modulabili e capacità emissiva allo stato solido: il bottle brush **3.2b** mantiene un'apprezzabile emissione nel rosso, e il PCL agisce da spaziatore sterico. + +I limiti del lavoro sono l'integrazione di DPP non superiore al 35%, l'esclusione di **3a** dall'innesto, la sottostima dei pesi molecolari da GPC e le discrepanze di **3.3c**, da indagare con ulteriori analisi. + +La prospettiva è l'impiego di questi materiali in dispositivi optoelettronici, in particolare come strato elettro-luminescente in OLED. + +**▶ CAMBIA SLIDE** + +## Slide 14 · Ringraziamenti (12:05 – 12:15) + +Ringrazio il relatore, i correlatori e tutti voi per l'attenzione. Sono a disposizione per le domande. + +--- + +## Durante la discussione: slide di scorta + +Dopo la slide 14 ci sono tre diapositive di scorta; per mostrarle torna indietro con le frecce o digita il numero della slide. + +| Slide | Quando usarla | +|---|---| +| 15 · UV-Vis ed emissione di **1** e **2** | domande sull'effetto dell'alchilazione: 531 → 541 nm per l'effetto induttivo donatore delle catene alifatiche, che destabilizza l'HOMO e restringe il band gap ottico | +| 16 · Pesi molecolari dei bottle brush | domande su GPC e NMR: i pesi da ¹H-NMR sono più vicini ai teorici di quelli da GPC | +| 17 · HOMO, LUMO e band gap | domande sui valori elettrochimici dei singoli campioni | diff --git a/presentazione/images/fig-film-copolimeri-uv.jpg b/presentazione/images/fig-film-copolimeri-uv.jpg new file mode 100644 index 0000000000000000000000000000000000000000..f445bfbb1b9d70a3ed8fe400b9d667b558cbba11 GIT binary patch literal 64701 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zwm%gxFTeHbo3-TiS2?Rehx5Z9d92q8XV#1@trO8C%=D5Hr!7K@H{R?m|AT zL-vq?4_M=Oc|e!Cbknn%Qh}KBP*fh7YI|i**_G&MskpBsa9(`VW50ra&)%Wr36hlm zLceICWz>snUB1E1CR-raGOnSmmsQ~>FOf-3Oh|>6WD_3jg!f*3P9}89@8Lvy-~a{>7Jr2!To{SEyAep z$k~;MqvqF=^LUKWt}?ZqFP-|UU>vj)t2d=4(mk}X4d(F`G`hmc5~e-17P=2BE;$7+N;HGK8T`yUaeV}K)bFxJ=FEIg5fD37_QeBR4>tm zle-pX>RleUD8Wa)Uo77~4nD}yacZcSMHSkKq-myye5B7t0oy-`S?D`aqU&fqgGDN= zoupNrreDJvm;+A|9fx)XXRpS|?wnT_Fta4YS@4q&1mS{wF1yC#p3&7GZ2VwdVz}g` z + + +## Tesi magistrale in Chimica Industriale · a.a. 2025-2026 + +# Sintesi e caratterizzazione di copolimeri bottle brush foto-elettro attivi + +**Candidata:** Aurora Luzi +**Relatore:** Dr. Stefano Scurti +**Correlatori:** Prof. Massimiliano Lanzi · Dr. Simone Gabellini · Dr. Riccardo Medri + +Dipartimento di Chimica Industriale "Toso Montanari" · Università di Bologna + +--- + +# ContestoSoft optoelectronics + +- **Semiconduttori organici π-coniugati**: leggeri, flessibili, depositabili da soluzione a bassa temperatura +- Convertono segnali elettrici in luce (**OLED**, diodi organici a emissione di luce) o viceversa (celle fotovoltaiche) +- Per usarli serve **ingegnerizzare il band gap** + +> **Approccio donatore-accettore (D-A)**: unità elettron-ricche ed elettron-deficienti alternate lungo lo scheletro → trasferimento di carica intramolecolare → assorbimento ed emissione nel visibile + +--- + +# Il problemaAggregation-Caused Quenching (ACQ) + +Lo scheletro π-coniugato è planare: le catene vicine si impilano (**π-stacking**). + +| | In soluzione | Allo stato solido | +|---|---|---| +| Catene | isolate dal solvente | vicine, π-stacking | +| Energia eccitonica | emissione | dissipazione non radiativa | +| Fluorescenza | presente | **smorzata (ACQ)** | + +> Nello strato emissivo di un OLED serve proprio l'emissione: l'ACQ ne limita le applicazioni + +--- + +# L'unità accettriceDichetopirrolopirrolo (DPP) + +![bg right:46% fit](images/fig1-dpp.jpg) + +- Nucleo **planare, rigido ed elettron-deficiente** +- π-stacking e legami a idrogeno → alta stabilità termica, ma **scarsa solubilità** +- **N-alchilazione**: elimina i legami H e aumenta la solubilità (×27 con un metile in DMF) +- Tiofeni in posizione 3 e 6: siti di **polimerizzazione** + +--- + +# Come legare il fluoroforoSistemi emissivi + +![bg right:50% fit](images/fig-sistemi-fluorofori.png) + +- **Host-guest**: migrazione e aggregazione dell'ospite +- **Cross-linked**: materiale fragile e insolubile +- **Side-chain** e **main-chain**: fluoroforo legato covalentemente +- **Grafting-from**: DPP con due OH innesca la ROP del PCL → PCL-DPP-PCL +- Qui: stessa strategia su scheletro **DPP-3HT** + +--- + +# ScopoStrategia bottle brush + +> Una architettura **bottle brush** può superare l'ACQ allo stato solido mantenendo l'integrità elettrochimica del core DPP? + +1. **Monomero ortogonale** derivato dal DPP +2. **Scheletro** DPP-3HT per polimerizzazione ossidativa +3. **Catene laterali** di PCL per ROP dell'ε-caprolattone +4. **Caratterizzazione**: ottica, strutturale, elettrochimica + +| Gruppo del monomero | Ruolo | +|---|---| +| Tiofeni | crescita dello scheletro (FeCl3) | +| Ossidrili (OH) | iniziatori della ROP: catene di PCL | + +--- + +# Fase 1Sintesi del monomero ortogonale + +![w:680](images/fig2-sintesi-dpp1.jpg) + +![w:760](images/fig3-alchilazione-dpp2.jpg) + +- **1**: ciclizzazione pseudo-Stobbe, 2-cianotiofene + diisopropil succinato +- **2**: N-alchilazione con 6-bromo-1-esanolo; 1H-NMR 4,1 e 3,6 ppm, FT-IR O-H ~3400 cm-1 + +--- + +# Fase 2Copolimerizzazione ossidativa con 3HT + +![w:960](images/fig4-copolimerizzazione.jpg) + +| Copolimero | % DPP teorica | % DPP reale | Mn (Da) | PD | +|---|---|---|---|---| +| **3a** | 20 | 25,2 | 2149 | 2,571 | +| **3b** | 50 | 32,6 | 1402 | 4,592 | +| **3c** | 80 | 35,3 | 2134 | 1,979 | + +- FeCl3 senza pre-funzionalizzazione; **DPP incorporato al massimo 35%** (reattività dei comonomeri) + +--- + +# Risultato intermedioCopolimeri lineari spenti allo stato solido + +![bg right:52% fit](images/fig-film-copolimeri-uv.jpg) + +- **In THF**: assorbimento 540-544 nm, emissione ~550 nm, come il monomero +- **Film solidi** sotto lampada UV: **nessuna emissione apprezzabile** +- DSC: Tg ~ −10 °C, nessuna fusione → copolimeri random + +→ ACQ confermata: serve il design **bottle brush** + +--- + +# Fase 3ROP dell'ε-caprolattone: i bottle brush + +![w:960](images/fig5-rop-bottle-brush.jpg) + +| Polimero | Mn PCL teorico (Da) | Mn GPC (Da) | PD | +|---|---|---|---| +| **3.1b** · **3.1c** | 1500 | 12188 · 13999 | 1,521 · 1,301 | +| **3.2b** · **3.2c** | 5000 | 17302 · 19119 | 1,314 · 1,275 | +| **3.3b** · **3.3c** | 10000 | 21269 · 14445 | 1,238 · 1,351 | + +- Innesto: 1H-NMR PCL a ~4,0 ppm; FT-IR scompare O-H, compare C=O estereo ~1720 cm-1 + +--- + +# Fase 4 · proprietà ottichePCL come spaziatore sterico + +![bg right:48% fit](images/fig6-uv-em-3.2b.jpg) + +**In THF** (tutti i bottle brush): assorbimento 544-554 nm, emissione 557-564 nm, Stokes shift 8-14 nm → **core DPP integro** + +**3.2b, stato solido** +- Assorbimento 570-580 nm (da ~550 nm) +- Emissione **650-660 nm**, Stokes shift ~80-90 nm +- Aggregati H e J, ma **emissione nel rosso mantenuta** + +--- + +# Fase 4 · proprietà elettrochimicheBand gap regolabile con la composizione + +![bg right:46% fit](images/fig7-bandgap-vs-dpp.jpg) + +- Ciclovoltammetria: HOMO, LUMO e **band gap elettrochimico** +- Copolimeri lineari: da **0,970 a 1,371 eV** all'aumentare del DPP reale (25,2 → 35,3%), andamento lineare +- Il DPP stabilizza il LUMO e favorisce l'iniezione di elettroni +- **Bottle brush: 0,929-1,521 eV**, elettroattività conservata: redox sul core, PCL come matrice dielettrica + +--- + +# ConclusioniRisultati, limiti e prospettive + +### Risultati +- Tre copolimeri statistici e due serie di bottle brush con PCL di 1500, 5000 e 10000 Da +- Il **3.2b** mantiene emissione nel rosso allo stato solido: il PCL è uno **spaziatore sterico** +- Il **band gap** è controllabile dalla composizione monomerica + +### Limiti +- DPP ≤ 35%; 3a escluso dall'innesto; GPC sottostima i pesi molecolari; 3.3c da approfondire + +### Prospettive +- Strato elettro-luminescente in **OLED** + +--- + + + + +# Grazie per l'attenzione + +Aurora Luzi + +--- + + + +# Diapositive di scortaUV-Vis ed emissione dei DPP 1 e 2 in THF + +![w:520](images/fig-uv-dpp1.jpg) ![w:520](images/fig-uv-dpp2.jpg) + +**1**: assorbimento 531 nm, emissione 542 nm, Stokes shift 11 nm · **2**: assorbimento 541 nm (effetto induttivo delle catene alifatiche) + +--- + + + +# Diapositive di scortaBottle brush: pesi molecolari + +| Polimero | Mn PCL teorico (Da) | Mn GPC (Da) | PD | Peso mol. teorico (Da) | Peso mol. da 1H-NMR (Da) | +|---|---|---|---|---|---| +| **3.1b** | 1500 | 12188 | 1,521 | 6500 | 8900 | +| **3.2b** | 5000 | 17302 | 1,314 | 18000 | 20500 | +| **3.3b** | 10000 | 21269 | 1,238 | 34500 | 88000 | +| **3.1c** | 1500 | 13999 | 1,301 | 10000 | 18200 | +| **3.2c** | 5000 | 19119 | 1,275 | 28500 | 35500 | +| **3.3c** | 10000 | 14445 | 1,351 | 55000 | 41300 | + +GPC (standard di polistirene lineare) sottostima: i polimeri ramificati sono compatti in soluzione. + +--- + + + +# Diapositive di scortaHOMO, LUMO e band gap elettrochimici + +| Polimero | HOMO (eV) | LUMO (eV) | Bandgap (eV) | +|---|---|---|---| +| **3a** | -5,038 | -4,068 | 0,970 | +| **3b** | -4,854 | -3,538 | 1,316 | +| **3c** | -4,799 | -3,428 | 1,371 | +| **3.1b** | -4,617 | -3,580 | 1,037 | +| **3.2b** | -4,625 | -3,527 | 1,098 | +| **3.3b** | -4,630 | -3,598 | 1,032 | +| **3.1c** | -4,774 | -3,253 | 1,521 | +| **3.2c** | -4,688 | -3,269 | 1,419 | +| **3.3c** | -4,479 | -3,550 | 0,929 |