Energy Transfer Processes in Polynuclear Lanthanide Complexes

153 Pages·2019·5.653 MB·English

by  Shun Omagari

Springer Theses
Recognizing Outstanding Ph.D. Research
Shun Omagari

Energy Transfer
Processes in
Polynuclear
Lanthanide
Complexes
Springer Theses
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Shun Omagari
Energy Transfer Processes
in Polynuclear Lanthanide
Complexes
Doctoral Thesis accepted by
Hokkaido University, Sapporo, Japan
123
Author Supervisor
Dr. ShunOmagari Prof. Dr. Yasuchika Hasegawa
Graduate Schoolof Chemical Faculty of Engineering
Sciences andEngineering Hokkaido University
Hokkaido University Sapporo,Hokkaido,Japan
Sapporo,Hokkaido,Japan
ISSN 2190-5053 ISSN 2190-5061 (electronic)
SpringerTheses
ISBN978-981-13-6048-0 ISBN978-981-13-6049-7 (eBook)
https://doi.org/10.1007/978-981-13-6049-7
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’
Supervisor s Foreword
Lanthanide physics and chemistry have been studied ever since the discovery of
rare earth elements in 1787 by C. A. Arrhenius, and extensive research on the
photophysical properties of lanthanide compounds came later, after the ground-
breaking theoretical works independently by B. R. Judd and G. S. Ofelt in 1962
(now known as the Judd–Ofelt theory). The high chromaticity and the long emis-
sion lifetimes of lanthanides are of particular importance in current technologies
involvingemissionoflight,rangingfromcommercializedtechnologieslikelighting
and telecommunication to research technologies like bioprobes and lasers.
Combinedwithcoordinationchemistry,otherwisepoorlylight-emittinglanthanides
can be enhanced into strongly light-emitting lanthanide complexes. The research
fieldoflanthanidecomplexesisofgreatinteresttodaywithmorethan1700papers
being published annually.
ThequestforaPh.D.degreeinchemistryisdauntingforthemanybecauseofthe
competitiveness,therequirementoffulldedication,andtherelativelylongduration
ofthecourse.However,thisdidnotpreventShunOmagarifromembarkingonthis
quest, associated with the goal of unraveling the luminescence mechanism of
polynuclear lanthanide complexes involving energy transfer. Specifically, the goal
was about understanding the luminescence mechanism of lanthanide clusters, a
polynuclear lanthanide complexwithlanthanides “core” and ligands “shell.”
Recently,polynuclearlanthanidecomplexesareconsideredasapromisingclass
ofluminescentmaterialduetotheenergytransferbetweenlanthanideionsthatgive
rise to new photofunctions such as temperature sensing, local probes, dual emis-
sion,andupconversion.Simultaneously,theadditionalprocessesleadtodifficulties
in analyzing the luminescence mechanism. Most reports on this topic usually
involve a practical approach; they discuss the luminescence mechanism based on
many experimental results and empirical evidence from other reports.
Shun took a different approach in his study, motivated by his fascination for
physics and mathematics. He overcame the theoretical difficulties by carefully
examining the Judd–Ofelt theory and kinetic analyses to reduce complicated
problemsintoasimplerformanddeliberatelydesignedtheexperiments.Thethesis
firstinvestigatedthefundamentaleffectofenergytransferbetweenYb3+ionsonthe
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emission lifetimes of Yb coordination polymers. A qualitative (and quantitative
with some assumptions) agreement was achieved between theoretical and experi-
mental emission lifetimes when phonon-assisted energy transfer was taken into
account.
The thesis also investigates the basic photophysical properties of nonanuclear
lanthanide clusters. This includes the effect of spin–orbit coupling induced by the
intrinsic angular momentum of electrons in Gd3+, Lu3+, and Yb3+ ions on the
energytransferefficiencyfromtheorganicligandstoYb3+ions.Theresultwasthat
a spin–orbit coupling too strong could reduce the energy transfer efficiency, con-
trary to the convention that the stronger the spin–orbit coupling always leads to a
better the energy transfer efficiency. The effect of back energy transfer (lanthanide
toorganicligands)wasalsoinvestigatedinTbclusters.Itwasrevealedthatthereis
anactivationenergyintheenergytransferbetweenlanthanideandorganicligands,
and the frequency factor that determine the coupling strength between the two
excited states.
Finally, the thesis combines the previous three conclusions and investigates the
effectofenergytransferbetweenTb3+ionsonbackenergytransferinnonanuclear
Tb clusters. The striking result was that the energy transfer between Tb3+ ions
mitigates the effect of back energy transfer by transferring the energy to a more
efficientlyemittingTbsite.Itwasalsofoundthattheeffectisespeciallyprominent
for clusters due to its structure. The thesis provides a new insight that lanthanide
clustersarepotentiallyanewclassofefficientlyluminescentfunctionalmaterial,as
well as fundamental insights into energy transfer processes in lanthanide com-
plexes.Themethodologyisalsothoroughlyexplainedinthethesisthatwillserveas
a useful reference for those working in this field of research.
Sapporo, Japan Prof. Dr. Yasuchika Hasegawa
August 2018
Parts of this thesis have been published in the following journal articles:
1. Omagari S, Nakanishi T, Kitagawa Y, Seki T, Fushimi K, Ito H, Meijerink A,
Hasegawa Y (2018) Spin-orbit Coupling Dependent Energy Transfer in
Luminescent Nonanuclear Yb-Gd / Yb-Lu Clusters. J Lumin 201:170–175.
https://doi.org/10.1016/j.jlumin.2018.04.049
2. Omagari S, Nakanishi T, Hirai Y, Kitagawa Y, Seki T, Ito H, Hasegawa Y
(2018) Origin of Concentration Quenching in Ytterbium Coordination
Polymers: Phonon-Assisted Energy Transfer. Eur J Inorg Chem 561–567.
https://doi.org/10.1002/ejic.201701396
3. Omagari S, Nakanishi T, Hasegawa Y et al (2016) Critical Role of Energy
Transfer Between Terbium Ions for Suppression of Back Energy Transfer in
Nonanuclear Terbium Clusters. Sci Rep 6:37008. https://doi.org/10.1038/
srep37008
4. Omagari S, Nakanishi T, Kitagawa Y, Seki T, Fushimi K, Ito H, Meijerink A,
Hasegawa Y (2015) Effective Photosensitized Energy Transfer of Nonanuclear
Terbium Clusters Using Methyl Salicylate Derivatives. J Phys Chem A
119:1943–1947. https://doi.org/10.1021/jp512892f
5. Omagari S, Nakanishi T, Kitagawa Y, Fushimi K, Hasegawa Y (2015)
Synthesis and Photoluminescence Properties of Nonanuclear Tb(III) Clusters
withLongAlkylChainGroup.e-JSurfSciNanotech13:27–30.https://doi.org/
10.1380/ejssnt.2015.27
Other publications by the author:
1. Dalafu H A, Rosa N, James D, Asuigui D R C, McNamara M, Kawashima A,
Omagari S, Nakanishi T, Hasegawa Y, Stoll S L (2018) Solid-State and
Nanoparticle Synthesis of EuSxSe1–x Solid Solutions. Chem Mater 30:2954–
2964. https://doi.org/10.1021/acs.chemmater.8b00393
2. Morisue M, Omagari S, Ueno I, Nakanishi T, Hasegawa Y, Yamamoto S,
Matsui J, Sasaki S, Hikima T, Sakurai S (2018) Fully Conjugated Porphyrin
Glass: Gollective Light-Harvesting Antenna for Near-Infrared Fluorescence
beyond 1 lm. ACS Omega 3:4466–4474. https://doi.org/10.1021/acsomega.
8b00566
3. FiaczykK,OmagariS,MeijerinkA,ZychE(2018)TemperatureDependenceof
4fn−15d1!4fn Luminescence of Ce3+ and Pr3+ Ions in Sr GeO Host. J Lumin
2 4
198:163–170. https://doi.org/10.1016/j.jlumin.2018.02.034
4. Seki T, Tokodai N, Omagari S, Nakanishi T, Hasegawa Y, Iwasa T,
Taketsugu T, Ito H (2017) A Luminescent Mechanochromic 9-Anthryl Gold(I)
Isocyanide Complex with an Emission Maximum at 900 nm after Mechanical
Stimulation. J Am Chem Soc 139:6514–6517. https://doi.org/10.1021/jacs.
7b00587
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viii Partsofthisthesishavebeenpublishedinthefollowingjournalarticles:
5. Watanabe A, Kobayashi A, Satoh E, Nagao Y, Omagari S, Nakanishi T,
Hasegawa Y, Sameera W M C, Yoshida M, Kato M (2017) Development of
Ion-Conductive and Vapoluminescent Porous Coordination Polymers
ComposedofRuthenium(II)Metalloligand.InorgChem56:3005–3013.https://
doi.org/10.1021/acs.inorgchem.6b03123
6. Murakami K, Ooyama Y, Watase S, Matsukawa K, Omagari S, Nakanishi T,
Hasegawa Y, Inumaru K, Ohshita J (2016) Chem Lett 45:502–504. https://doi.
org/10.1246/cl.160036
7. Kataoka H, Nakanishi T, Omagari S, Takabatake Y, Hasegawa Y (2016)
Drastically Improved Durability and Efficiency of Silicon Solar Cells Using
Hyper-Stable Lanthanide Coordination Polymer Beads. Bull Chem Soc Jpn
89:103–109. https://doi.org/10.1246/bcsj.20150325
8. Kataoka H, Omagari S, Nakanishi T, Hasegawa Y (2015) Photo-degradation
Analysis of Luminescent Polymers with Lanthanide Complexes. J Photopolym
Sci Technol 28:247–254. https://doi.org/10.2494/photopolymer.28.247
9. Kataoka H,OmagariS,NakanishiT,HasegawaY(2015)EVAThinFilmwith
Thermoo- and Moisture-stable Luminescent Copolymer Beads Composed of
Eu(III)ComplexesforImprovementofEnergyConversionEfficiencyonSilicon
SolarCell.OptMater42:411–416.https://doi.org/10.1016/j.optmat.2015.01.038
Acknowledgements
Throughout my five years that I have been in the Advanced Materials Chemistry
Laboratory(AMCLaboratory),thereweremanygreatexperiencesthatchangedmy
life. Such experiences are not limited to research, but social life, friendship,
responsibility, hardships, etc., as a matter of fact, everything. The people of the
AMC Laboratory become the central part of my life and have influenced me in
every way possible. It is thus inevitable that my Ph.D. degree had tremendous
contributions from the people around me. Below is my attempt at showing my
greatest appreciation toward those that have contributed to my Ph.D. thesis.
First and foremost, I would like to express my sincere gratitude to my main
advisors, Prof. Yasuchika Hasegawa, Ph.D., and Prof. Takayuki Nakanishi, Ph.D.,
oftheAMCLaboratory.ProfessorNakanishiinparticular,myprimaryadvisor,has
supervised me for the five years that I was in the laboratory (including under-
graduate).Iamproudtobethefirstonetograduatethemaster’scourseunderhim,
and now the Ph.D. course. In terms of research, he and I had a very different
approach, and yet, he still granted me the freedom to choose the style I feel I am
good at. Professor Hasegawa is the reason why I decided to join this laboratory in
the first place. I thank him for granting me the place to do what I can do. My
advisorswereverysupportiveofmyacademiccareerandgoals.Theywerealsothe
ones that stopped me when I have gone too far with my curiosity, which was
crucially important to produce meaningful results. This thesis would never have
even begun without them.
I would also like to express my gratitude toward my other advisors, Prof. Koji
Fushimi,Ph.D.,andProf.YuichiKitagawa,Ph.D.,oftheAMCLaboratoryaswell
as Prof. Noboru Kitamura, Ph.D., of the Analytical Chemistry Laboratory. I thank
thethreefortheiracademicdiscussions.Ithasgreatlyhelpedmeapproachscience.
ProfessorFushimi’sguidanceinacademicwritingwasalsocrucialforpolishingmy
works. Quantum chemical discussions of excited states with Prof. Kitagawa and
Prof. Kitamura gave me a good sense of scientific understanding of various pho-
tophysical phenomena.
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