University of Groningen
Chromism of spiropyrans
Kortekaas, Luuk
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Publication date: 2018
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Kortekaas, L. (2018). Chromism of spiropyrans: from solutions to surfaces. University of Groningen.
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CHROMISM OF SPIROPYRANS
From solutions to surfaces
The work described in this thesis was carried out at the Molecular Inorganic Chemistry department of the Stratingh Institute for Chemistry, University of Groningen, The Netherlands.
The work reported in this thesis was supported financially by the Ministry of Education, Culture and Science (Gravitation program 024.001.035).
Printed by: Ipskamp Drukkers, Enschede, The Netherlands
Cover artwork: “Herakles the Archer” by Antoine-Émile Bourdelle, as on view at the Metropolitan Museum of Art in New York City.
ISBN: 978-94-034-0720-3 (printed version) ISBN: 978-94-034-0719-7 (electronic version)
CHROMISM OF SPIROPYRANS
From solutions to surfaces
PhD thesis
to obtain the degree of PhD at the
University of Groningen
on the authority of the
Rector Magnificus Prof. E. Sterken
and in accordance with
the decision by the College of Deans.
This thesis will be defended in public on
Monday the 25
thof June 2018 at 11.00 hours
by
Luuk Kortekaas
born on the 13
thof May 1990
Supervisors
Prof. Dr. W.R. Browne
Prof. Dr. B. L. Feringa
Assessment committee
Prof. Dr. S. E. J. Bell
Prof. Dr. M. Venturi
Prof. Dr. S. Otto
Table of Contents
Chapter 1 - Spiropyrans: a Versatile Class of Photochromes That Keeps Surprising
Introduction ... 2
Spiropyrans before they were excited ... 2
Thermochromism of spiropyrans ... 4 Solvatochromism of spiropyrans ... 7 Photochromism of spiropyrans ... 9 Fluorescence of spiropyrans ... 12 Acidochromism of spiropyrans ... 13 Redox-properties of spiropyrans ... 14 Concluding remarks ... 17 Outlook ... 19 References ... 20
Chapter 2 - Reversible Charge Trapping in bis-Carbazole-Diimide Redox Polymers with Complete Luminescence Quenching Enabling Nondestructive Read-out by Resonance Raman Spectroscopy Introduction ... 24
Experimental section ... 28
Materials. ... 28
Physical Methods. ... 28
Results and Discussion ... 29
UV/vis absorbance and emission spectroscopy ... 29
Electrochemical modulation of Poly-APCCDI Fluorescence ... 32
Multiresponsive bis-carbazole based redox polymer films incorporating naphthalene diimide. 32 Resonance Raman spectroscopy of APCNDI ... 34
Cyclic Voltammetry of APCNDI ... 34
UV/vis-NIR absorption spectroelectrochemistry of poly-APCNDI ... 36
Resonance Raman spectroelectrochemistry of poly-APCNDI ... 36
Conclusions ... 40
References ... 40
Chapter 3 - Solvation Dependent Redox-Gated Fluorescence Emission in a Diarylethene Based Sexithiophene Polymer Film Introduction ... 46
Experimental Section ... 48
Materials. ... 48
Physical Methods. ... 48
Results and discussion ... 48
Conclusion ... 54
References ... 56
Chapter 4 - A Remarkable Multitasking Double Spiropyran: Bidirectional Visible-Light Switching of Polymer-Coated Surfaces with Dual Redox and Proton Gating Introduction ... 60
Experimental Section ... 64
Materials. ... 64
Physical Methods. ... 65
Results and discussion ... 66
pH gated photochromism. ... 66
UV/vis/NIR absorption spectroelectrochemistry. ... 68
Synthesis and characterization. ... 70
Cyclic voltammetry at polymer modified electrodes. ... 71
Vis/NIR absorption spectroelectrochemistry of spiropyran polymers. ... 72
Photochromism of spiropyran polymers. ... 73
UV/vis absorption spectroelectrochemistry of photoswitched polymer2+. ... 73
Electrochemically gated switching of spiropyran polymers. ... 74
Summary and Conclusions ... 74
Chapter 5 - Proton Stabilized Photochemically Reversible E/Z Isomerization of Spiropyrans
Introduction ... 80
Experimental Section ... 82
Materials ... 82
Physical Methods ... 83
Results and Discussion ... 83
Acidochromism of SP and NSP with weak acids ... 83
pH-gated photochromism of SP and NSP with strong acids ... 84
Calculated energies and barriers for ring opening of SP and NSP ... 86
Re-enabling room temperature switching of SP ... 87
Conclusions ... 88 Supporting information ... 89 Physical Methods ... 95 Actinometry ... 95 Supporting Figures ... 97 Theoretical Methods ... 102 References ... 104
Chapter 6 - Novel Reactivity in Bispiropyran Photochromes Introduction ... 108
Experimental section ... 110
Materials. ... 110
Physical methods. ... 111
Results and Discussion ... 111
Photochromism of bispiropyrans ... 112
pH-gating and acidochromism of bispiropyrans ... 112
pH-gating of photo induced extended conjugation in bispiropyrans ... 113
1 H NMR spectroscopy of bispiropyrans ... 114
1 H NMR spectroscopy at -30 oC with in situ irradiation ... 116
Fluorescence spectroscopy of bispiropyrans ... 118
Conclusions ... 118
Supporting information ... 119
Chapter 7 - Redox-Chemistry of Bispiropyrans
Introduction ... 124
Experimental section ... 125
Materials ... 125
Physical methods ... 126
Results and Discussion ... 126
Cyclic Voltammetry ... 126
Spectroelectrochemistry ... 130
Concluding Remarks and Future Prospects ... 131
References ... 132
Summary... 133
Samenvatting ... 136
Acknowledgements ... 140
