Synthesis of Quaterrylene-Based Dyes for NIR Dye-Sensitized Solar Cells

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Synthesis of Quaterrylene-based Dyes for NIR

Dye-Sensitized Solar Cells

Marco Giordano,

a

_{A. Fin,}

b

_{M. Bonomo,}

a

_{N. Barbero,}

a

_{C. Barolo,}

a

_{G. Viscardi}

a

_{Dipartimento di Chimica, NIS Interdepartmental and INSTM Reference Centre, Università di Torino, Torino, Italy}

b

_{Dipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Torino, Italy}

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1 Why exploit the NIR radiation?

N. Barbero, F. Sauvage, in Materials for Sustainable Energy Applications: Conversion, Storage, Transmission and Consumption, CRC Press, 2016, 87-147 http://h.glass/products/ and https://impressive-h2020.eu/

BIPV

Co-sensitization

VG20

C106

NIR-DSSC

Colourless

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N. Barbero, F. Sauvage, in Materials for Sustainable Energy Applications: Conversion, Storage, Transmission and Consumption, CRC Press, 2016, 87-147 A. Alagumalai, M. K. M. Fairoos, P. Vellimalai, M. Chandra Sil, J. Nithyanandhan, ACS Appl. Mater. Interfaces 2016, 8, 35353−35367

M. Kimura, H. Nomoto, N. Masaki, S. Mori, Angew. Chem. Int. Ed. 2012, 51, 4371–4374

2 NIR-dyes in DSSCs

Strongly absorption beyond 700 nm

Poor solubility

High thermal and chemical stability

Not negligible absorption band in the

visible region (ɛ > 15000)

3,1%

VG20-C16

Phthalocyanines

PcS18

5,9%

SQ5

9,0%

Squaraines

Cyanines

Polymethine-based dyes

Some squaraines dyes have not negligible

absorption band in the visible region (ɛ > 15000)

Strongly absorption beyond 700 nm

Easy synthesis

Polymethine dyes present yet regeneration issues

with the common cobalt-based redox couples

To know more about

polymethine dyes, don't

miss the Prof. Barolo’s talk!

DSSC

2.1 – i2

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3 Rylene-based dyes in DSSCs – PDIs

Outstanding photochemical

and thermal stability

Strongly absorption band

around 500 nm

Easy

tunability

of

photophysical properties

Strongly

π-π

stacking

interaction

C. Li, J. H. Yum, S. J. Moon, A. Herrmann, F. Eickemeyer, N. G. Pschirer, P. Erk, J. Schoeboom, K. Müllen, M. Gratzel, M. K. Nazeeruddin, ChemSusChem 2008, 1, 615–618. C. Li, H. Wonneberger, Adv. Mater. 2012, 24, 613–636.

First

generation

Second

generation

Functionalization of

the rylene core

Extension of the

rylene core

Toward

the NIR

Toward

the NIR

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4 The extended rylene-dyes

X. Zhao, Y. Xiong, J. Ma, Z. Yuan, J. Phys. Chem. A 2016, 120, 7554−7560. L. Chen, C. Li, K. Müllen, J. Mater. Chem. C 2014, 2, 1938–1956.

λ

_MAX

> 700 nm

Suitable HOMO level around -5,25 eV

Suitable LUMO level around -3,75 eV

Soluble in chlorinated solvents

QDI

5DI

_QDI

5DI

n = 2 Quaterrylene-based dyes (QDI)

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5 First synthetic

strategy

Functionalization

Extension

Hydrolysis

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6 Why we changed strategy?

Poor selectivity

Difficult purification

Non-scalable

reaction:

dangerous!

Very low yield (4a)

Difficult purification

Synthesis

of

4b

is

impossible: we isolated only

the

mono-functionalized

compound

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7 Functionalization

Extension

Second synthetic

strategy

Hydrolysis

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8 Core extention – The building blocks

Reaction scale-up it’s

easy and safety

High selectivity

Quantitative yield

Reaction scale-up it’s easy

Y. Geerts, H. Quante, H. Platz, R. Mahrt, M. Hopmeier, A Böhm, K Müllen, J. Mater. Chem., 1998, 8, 2357–2369.

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High yield

Easy purification

Multi-step procedure

Single step procedure

Low yield

238 nm

λ=529 nm

λ=767 nm

ESI-MS

1

_H-NMR

Core extention – The QDI’s formation

9

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10 Core functionalization

Y. Avlasevich, S. Müller, P. Erk, K. Müllen, Chem. Eur. J. 2007, 13, 6555–6561.

Very soluble in chlorinated

solvents

Poor selectivity

Non-scalable

reaction:

dangerous!

420 eq. of

bromine are need)

Very soluble in chlorinated

solvents

The

product

was

isolated

as

a

regioisomers mixture

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17 on TiO

2

(6 μm on FTO)

11 Hydrolysis and

preliminary study

λ=767 nm

λ=770 nm

17

20

Band gap (Energy) / eV 1.63 1.61

HOMO / eV -5.54 -5.64 LUMO / eV -3.71 -3.92 Mono-Hydrolisis confirmed by MALDI-TOF experiment