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«A DISSERTATION SUBMITTED TO MATERIALS SCIENCE AND NANOTECHNOLOGY PROGRAM OF THE GRADUATE SCHOOL OF ENGINEERING AND SCIENCE OF BILKENT UNIVERSITY IN ...»

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CHIRAL BODIPY DYES & PHOTOSENSITIZERS FOR

PHOTODYNAMIC THERAPY AND DYE SENSITIZED SOLAR

CELLS

A DISSERTATION SUBMITTED TO

MATERIALS SCIENCE AND NANOTECHNOLOGY PROGRAM

OF THE GRADUATE SCHOOL OF ENGINEERING AND SCIENCE

OF BILKENT UNIVERSITY

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS

FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

By

YUSUF ÇAKMAK

February, 2013 I certify that I have read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis of the degree of Doctor of Philosophy.

………………………………….

Prof. Dr. Engin U. Akkaya (Advisor) I certify that I have read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis of the degree of Doctor of Philosophy.

………………………………….

Assoc. Prof. Dr. Mehmet Bayındır I certify that I have read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis of the degree of Doctor of Philosophy.

………………………………….

Assist. Prof. Dr. Serdar Atılgan ii I certify that I have read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis of the degree of Doctor of Philosophy.

………………………………….

Assist. Prof. Dr. Özgür Altan Bozdemir I certify that I have read this thesis and that in my opinion it is fully adequate, in scope and in quality, as a thesis of the degree of Doctor of Philosophy.

………………………………….

Assist. Prof. Dr. Tamer Uyar

Approved for the Graduate School of Engineering and Science:

………………………………….

Prof. Dr. Levent Onural Director of the Graduate School iii

ABSTRACT

CHIRAL BODIPY DYES & PHOTOSENSITIZERS FOR

PHOTODYNAMIC THERAPY AND DYE-SENSITIZED SOLAR

CELLS Yusuf Çakmak PhD in Materials Science and Nanotechnology Supervisor: Prof. Dr. Engin U. Akkaya February, 2013 Bodipy is a molecule with many superior properties. After its discovery in 1968, most of the features were not recognized until mid 1990s. Thereafter, many research papers and patents have been produced and the number of publications and citations is still on the rise today. An important fraction of the research done with this fluorophore is in chemosensing field to probe various analytes including anions, cations and even biomolecules. However, in this research we have focused on different areas of subjects and tried to find novel applications for these dyes. First, we designed orthogonal bodipy dimers for efficient triplet photosensitization without heavy atoms in contrast to most other sensitizers and efficient singlet oxygen generation was achieved (Φ∆=0.51). In the second project, calix[4]arene molecules were designed and synthesized as carriers for photodynamic therapy, potentially behaving as a molecular basket carrying the agents to the tumor tissues. Later, we focused on obtaining axial chiral molecules by using solely bodipy dyes, and we were able to obtain enantiopure fragments were separated by using chiral HPLC.

These rare molecules are desirable for modern biological labeling and advanced optoelectronic devices. Finally, we designed bodipy dyes for dye sensitized solar cells by adapting relevant functional groups, and following synthesis work, we constructed cells to assess the design parameters via measuring the electrical output results.

Keywords: Photodynamic therapy, triplet photosensitization, axial chirality, dye sensitized solar cell, singlet oxygen

–  –  –

KİRAL BODIPY BOYALARI & FOTODİNAMİK TERAPİ VE BOYA

DUYARLILAŞTIRILMIŞ GÜNEŞ PİLLERİ İÇİN

FOTODUYARLILAŞTIRICILAR

–  –  –

Bodipy üstün özelliklere sahip olan bir moleküldür. 1968 yılında keşfedilmesinden sonra 1990’lı yılların ortalarına kadar özelliklerinin büyük bir kısmı bilinmiyordu. Sonrasında ise, oldukça fazla sayıda bilimsel makale ve patent üretilmiştir, bugün bile bu boya ile ilgili makale sayısı ve atıf sayısı hızlı artmaktadır.

Bu madde ile yapılan çalışmaların büyük kısmı anyonları, katyonları ve hatta biyomolekülleri algılama da kullanılmaktadır. Fakat, bu araştırmada biz bodipy molekülünün en iyi olmadığı fakat iyi olma potansiyeli olan diğer alanlara yoğunlaştık ve bodipy’i bu alanlara uygulamaya çalıştık. İlk olarak bir çoğunda olduğunun aksine ağır atom içermeyen dik bodipy dimerleri dizayn ettik ve etkili singlet oksijen üretimi elde ettik (ΦΔ=0.51). Bu konu altındaki ikinci projede kaliks[4]aren moleküllerini, fotodinamik terapi ajanları taşıyacak ve moleküler sepet gibi davranan hedefli bir ünite olarak tasarladık. Sonra, sadece bodipy moleküllerinden oluşan eksensel kiralite özelliği olan moleküllere yoğunlaştık ve enantiyosaf parçaları kiral HPLC kullanarak ayırmayı başardık. Bu nadir görülen maddeler modern biyolojik etiketlemede ve gelişmiş optoelektronik aygıtlar için talep edilmektedir. Son olarak, başarısı kanıtlanmış fonksiyonel grupları bodipy molekülüne uygulayarak boya duyarlılaştırılmış güneş pilleri için boyar madde tasarladık ve sentez ve pil yapımı aşamalarından sonra elektrik çıktı sonuçlarını ölçerek dizayn parametrelerini değerlendirdik.





Anahtar kelimeler: Fotodinamik terapi, triplet fotoduyarlılaştırma, eksensel kiralite, boya duyarlılaştırılmış güneş pili, singlet oksijen

v ACKNOWLEDGEMENT

I would like to thank to TÜBİTAK (The Scientific and Technological Research Council of Turkey) for giving me the opportunity of very beneficial abroad scholarship programme I would like to thank my supervisor Prof. Dr. Engin U. Akkaya whose encouragement and support made this study possible. I also want to express my sincere appreciation to him for his guidance, teaching, and understanding during this research.

I would like to thank Safacan Kölemen, Ziya Köstereli, Tuğrul Nalbantoğlu, Tuğçe Durgut for their patience, friendship and help during the projects which we worked with.

I want to thank our present group members Ruslan Guliyev, Onur Büyükçakır, Tuğba Özdemir, Fazlı Sözmen, Bilal Uyar, Ahmet Atılgan, Tuba Yaşar, Yiğit Altay, Bilal Kılıç, Esra Tanrıverdi, Nisa Yeşilgül, Ahmet Bekdemir, İlke Şimşek, the past members Gökhan Barın, Sencer &Hande Boyacı Selçuk and the other Akkaya group members for their valuable friendships, wonderful collaborations, and great ambiance in the laboratory. It was a great experience to work with them.

Also special thanks to Özgür Altan Bozdemir, Mahmut Deniz Yılmaz, Ali Coşkun, Serdar Atılgan and Erhan Deniz for their recommendations, comments and beautiful friendships starting from the very beginning of the research life.

I would like to express my sincere gratitude to Yavuz Dede, Muhammed Büyüktemiz, Şule Erten-Ela and Bora Bilgiç for their devoted help for the various subjects that make my thesis better.

My very special thanks go to my close friends and Mehmet Alp, Defne, Nilay&Osman, Alper, My Father, My Mother and the special person of my life Sündüs.

–  –  –

: Förster Resonance Energy Transfer FRET : Highest Occupied Molecular Orbital HOMO : Lowest Unoccupied Molecular Orbital LUMO : Matrix-Assisted Laser Desorption/Ionization MALDI

–  –  –

1 INTRODUCTION

2 BACKGROUND

2.1 Photodynamic Therapy

2.1.1 General Information

2.1.2 Development of PDT

2.1.3 The Mechanism and Methods of PDT

Mechanism of Singlet Oxygen Production64

2.1.4 2.1.5 Molecular Orbital Diagram of Triplet and Singlet Molecular Dioxygen65

2.2 Triplet Photosensitization

2.2.1 Heavy Atom Effect on Triplet Photosensitization

Triplet PSs with low-lying n-π* transitions

2.2.2 2.2.3 Exciton Coupling Behaviour of Chromophores

2.2.4 Utilizing Spin Converter for Triplet State Photosensitization............. 22 2.2.5 Methods to Detect Triplet Excited States

2.2.6 Triplet PSs recently studied

2.2.7 Triplet PSs without Heavy Atom

2.2.8 Employment of Triplet PSs

2.3 Asymmetry in Luminophores

2.3.1 Optical Spectroscopy

2.3.2 CD Spectroscopy

2.3.3 Atropisomerism

2.3.4 Bodipy Asymmetry

2.4 Dye Sensitized Solar Cell

2.4.1 General Information

2.4.2 Main types of organic dye based DSSCs

viii 2.4.

3 n-Type Semiconductor TiO2-based Type-I DSSCs

Solar Cell Photovoltaic Parameters112

2.4.4 3 Novel Sensitization in PDT with Bodipy Dyes

3.1 Theory-Guided Access to Efficient Photosensitizers by Heavy Atom Free Orthogonal Bodipy Dimers

3.1.1 Introduction

3.1.2 Theoretical Investigation

3.1.3 Design Principles

3.1.4 Synthesis Methodology

3.1.5 Singlet Oxygen Production

3.1.6 Cytotoxicity Experiments

3.1.7 Extended Conjugation of an Bis-BODIPY Derivative

3.1.8 Conclusion

3.1.9 Experimental Section

3.2 PEGylated Calix[4]arene as a Carrier for a Bodipy-based Photosensitizer 93 3.2.1 Introduction

3.2.2 Design and Synthesis

3.2.3 Results and Discussion

3.2.4 Conclusion

3.2.5 Experimental Details

4 Axial Chiral Bodipys

4.1 Introduction

4.2 Design And Synthesis

4.3 Separation And Photophysical & Circular Dichroism Characterization Of Enantiomers

4.4 Conclusion

4.5 Experimental Details

5 Thiophene Based PS’s For Dssc

ix

5.1 Introduction

5.2 Design and Synthesis:

5.3 Results and Discussion

5.4 Conclusion

5.5 Experimental Details

5.5.1 Device Fabrication:

5.5.2 Synthesis

6 Conclusion

7 Appendix

7.1 Theory-Guided Access to Efficient Photosensitizers by Heavy Atom Free Orthogonal Bodipy Dimers

H and 13C NMR Spectra

7.1.1 7.1.2 Mass Spectra

7.1.3 Size distribution analysis

7.1.4 Photophysical Measurements

7.2 PEGylated Calix[4]arene as a Carrier for a Bodipy-based Photosensitizer 7.2.1 H and C NMR Spectra

7.2.2 Mass Spectra

7.3 Axial Chiral Bodipys

H and 13C NMR Spectra

7.3.1 7.3.2 Mass Spectra

7.3.3 Absorbance and Emission Spectra

7.4 Thiophene Based Ps’s For Dssc

H and 13C NMR Spectra

7.4.1 7.4.2 Mass Spectra

x LIST OF FIGURES

Figure 1.Web citation report of the number of research papers and the citations when searched in the topic part “bodipy”

Figure 2. Modified Jablonski diagram for singlet oxygen production

Figure 3. Structure of Haematoporphyrin

Figure 4. Biosynthesis of protoporphyrin in mammals starting from aminolevunilic acid

Figure 5. Some biomolecules’ reaction with singlet oxygen and its products64.

....... 17 Figure 6. Molecular orbital diagram of molecular dioxygen with its ground and excited states65

Figure 7. Fluorescein and its halogenated derivatives as triplet PSs75

Figure 8. Diiodinated Bodipy for PDT76

Figure 9. Aza BODIPY derivative for PDT application

Figure 10. Naphtalene diimide molecule used for triplet photosensitization79.

......... 26 Figure 11. Simplified Jablonski diagram showing the photopysics of C60chromophore hybrids as heavy atom free triplet PSs

Figure 12. Fullerene-bodipy dyads as efficient heavy-atom-free organic triplet photosensitizers80

Figure 13. Heavy atom free small organic molecules as triplet PSs absorbing at UV region

Figure 14. di(Perylene Bisimide)s as PSs for singlet oxygen generation83.

............... 31 Figure 15. Exciton coupling behaviour of bis-bodipy triplet photosensitizers.

......... 32 Figure 16. Mechanism for the water splitting to produce H2.

Figure 17. Molecular Structures of the Platinum(II) Terpyridyl π-Conjugated.

........ 34 Figure 18. TTA upconversion process in modified Jablonski diagram

Figure 19. Structure of the Bodipy PS

Figure 20. Proposed reaction mechanism of visible-light-induced aerobic hydroxylation reaction92

Figure 21. Ratiometric O2 sensor

Figure 22. The combined effect of electronic and magnetic transition moments, which is the origin of chirality98

xi Figure 23. The electric vector of left circularly polarized light following an anticlockwise path. It rotates per wavelength along the axis of light propagation98.. 42 Figure 24. The ellipcity, θ

Figure 25. Axial chiral molecules

Figure 26. Chirality induced to phtalocyanine molecule by binaphtyl99

Figure 27. Structure of optically active fluorescent binaphtol appended bodipy100.

. 49 Figure 28. a) decrease of bodipy fluorescence with the addition of diisopropylethylamine in acetonitrile. b) Plots for the quenching of chiral hydroxyl binaphtol bodipy with S- and R- Phenylethylamine (PEA) in acetonitrile100............ 50 Figure 29. Boron asymmetry in bodipy molecule3

Figure 30. Circular Dichroism (CD) spectra

Figure 31. Working scheme and principles of n-type TiO2 DSSC (Type I)113.

......... 55 Figure 32. Equations showing the mechanism of photocurrent via n-type TiO2 based DSSC (Type I)113

Figure 33. Structure of Bodipy (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene).

......... 62 Figure 34. Frontier orbital plots and natural orbital occupation numbers (NOON) for the dimer OB3.

.

Figure 35. Conceptual frontier MO diagram



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