Joining Corroles and Phthalocyanines in functional porphyrinoid arrays

197 Pages·2017·5.78 MB·English

UNIVERSITÀ DEGLI STUDI DI ROMA “TOR VERGATA”
UNIVERSIDAD AUTÓNOMA DE MADRID

Joining Corroles and Phthalocyanines
in functional porphyrinoid arrays

Beatrice Berionni Berna

Supervisors:

Dr. Sara Nardis
Prof. Tomás Torres Cebada

Academic year 2016/2017

This work was developed as a joint PhD
between the Department of Chemical
Science and Technology of University of
Rome Tor Vergata, under the supervision of
Dr. Sara Nardis, and the Department of
Organic Chemistry of The Autonomous
University of Madrid, under the supervision
of Prof. Dr. Tomás Torres Cebada.

Thi•s w“oErxkt wenadsi pnrge stehnet ecdo rinro tlhee rfoinllgo wcoinngju agratitciolens:: preparation of β,β′ [1′,2′
-fused 2,3- -
Org. Biomol. Chem 2016
b]pyrazinocorroles”. B. Berionni Berna, S. Nardis, F. Mandoj, F. R. Fronczek, K.
M. Smith, R. Paolesse. ., ,14, 2891-2897
• “β

-Pyrrolopyrazino Annulated Corroles via a Pictet–Spengler Approach”. B.
Org. Lett. 2016
Berionni Berna, S. Nardis, P. Galloni, A. Savoldelli, M. Stefanelli, F.R. Fronczek,
K.M. Smith, R. Paolesse. , , 18, 3318–3321

Pre-doctoral stay:
•

Photophysical measurements were carried out in the group of Prof. Dirk M. Guldi
in the Department of Chemistry and Pharmacy of Friedrich-Alexander-
Universität of Erlangen-Nürnberg, Germany, May 2017.

Abbreviations and acronyms

J. Org. Chem. 2016
Abbreviation and acronyms used in this thesis are listed in the “guidelines for authors”
of , and can be found in the journal webpage:
http://pubs.acs.org/paragonplus/submission/joceah/joceah_authguide.pdf

A Acceptor
AcOH Acetic acid
Corr Corrole
CR Charge recombination
CS Charge separation
CSR Charge separation rate
CSS Charge separation state
CT Charge transfer
CV Cyclic voltammetry
D Donor
DBSA p-dodecylbenzenesulfonic acid
DCTB trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-
propenylidene]malononitrile
DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
DFT Density functional theory
DPM Dipyrromethane
DSSC Dye-sensitized solar cell
ε
ESI Electrospray ionization
Molar extinction coefficient
FAB Fast atom bombardment
G Guest
H Host
λ
HOMO Highest occupied molecular orbital
Wavelength
L Linker
LUMO Lowest unoccupied molecular orbital
o o
MALDI Matrix-assisted laser desorption ionization
-DCB -Dichlorobenzene
Φ
Quantum Yield
Pc Phthalocyanine
PET Photoinduced electron transfer
PHT Photoinduced hole transfer
Por Porphyrin
TBAH Tetrabutylammonium hexafluorophosphate
TBAP Tetrabutylammonium perchlorate
TFA Trifluoroacetic acid
THF Tetrahydrofurane
TMS Trimethylsilyl
Table of Contents

Summary….……………………………………………………………………………………………...………….……I
Riassunto…………………………………………………………………………………………………………...…VII
Resumen………………………………………………………………………………………………………..…….XIII
I ntroduction
Errore. Il segnalibro non è definito.
…………………………………………….………………………………………………………….1

Corroles………………………………………………………………………………………………………………..3
meso
Structure and General Properties…………………………………………………………………...…..5
3
Synthesis of -substituted A Corroles…………………………………...……………………10
2 3
Synthesis Using Al O as a Solid Support………………………………………………………..11
Modified Rothemund method………………………………………………………………………..12
Modified Král method…………………………………………………………………………………...13
Modified Lindsey method……………………………………………………………………………...12
meso

2
Synthesis of -substituted trans A B Corroles……………………………………………..13
Corrole-based applications………………………………………………………………………………….16
References……………………………………………………………………………………………………….…19
General Objectives

Errore. Il segnalibro non è definito.
……………………………………………………….…………………..…….…...…...25

Thesis distribution………………………………………………………………………………………………27
Chapter I
Errore. Il segnalibro non è definito.
1 ………………………………………………………………………………………………………..…29

State of the Art………………………………………………………………………………………….…………30
Functionalization of aminocorroles………………………………………………………….…………..36
Nitration…………………………………………………………………………………………….……………37
Amination……………………………………………………………………………………………….……….41
Results and discussion…………………………………………………………………………….…………..44
Functionalization by one- pot reduction and condensation………………………………..44
Reaction with 1,2-cyclohexanedione……………………………………………………………...46
Reaction with 1,4-dibromo-2,3-butanedione and further functionalization……..51
Reaction with 9,10-phenanthrenequinone……………………………………………………..55
Demetalation………………………………………………………………………………………………..57
Catalytic hydrogenation and condensation……………………………………………………58
Synthesis of a pyrrole moiety via a Clauson−Kaas reaction………………………….….64
Functionalization via Pictet–Spengler approach……………………………………………..….64
π extended β,β'

- -copper (II) pyrrolo[1,2-a]pyrazinocorrolates via a
Pictet-Spengler reaction………………………………………………………………………….……67
Vilsmeier-Haack formilation of 2-(pyrrol-1-yl)-3-nitro corrolate……………………73
Summary and conclusions…………………………………………………………………………………...75
Experimental section…………………………………………………………………………………………..77
Materials and Instruments……………………………………………………………………………….77
Synthetic procedures……………………………………………………………………………………….78

References………………………………………………………………………………………………………….90
Chapter II
2. ……………………………………………………………………………………………….……95

The Energy Issue…………………………………………………………………………………………………97
Basic theory of photoinduced Electron Transfer (PET) and Excited Energy
Transfer (EET)…...……………………………………………………………………………...…………….98
Marcus theory of electron transfer………………………………………………………………….101
Phthalocyanines………………………………………………………………………………...……………...103
Synthesis of Phthalocyanines……………………………………………………………......………..105
Synthesis of symmetrically substituted phthalocyanines………………………………105
Synthesis of asymmetrically substituted phthalocyanines………………………….…106
Phthalocyanines as organic synthetic artificial photosystems…………………………..107
Results and discussion………………………………………………………………………………………109
Pthalocyanine-Corrole covalent systems…………………………………………………………109
Synthesis of ethynylphenyl-substituted corroles…………………………………….……110
Synthesis of monoiodo-phthalocyanine derivative……………………………………….113
Assembly of Corr-ZnPc dyads……………………………………………………………………...114
Electrochemical Studies………………………………………………………………………………116
Calculation of HOMO-LUMO levels……………………………………………………………….119
DFT B3LYP/3-21G(*) Calculations……………………………………………………….……...120