Development of Synthetic Methods for Novel Photofunctional Multinuclear Complexes: Simple Synthetic Methods for Multinuclear Complexes Using Various C-C Coupling Reactions

115 Pages·2021·5.24 MB·English

by  Yasuomi Yamazaki

Springer Theses
Recognizing Outstanding Ph.D. Research
Yasuomi Yamazaki
Development
of Synthetic
Methods for Novel
Photofunctional
Multinuclear
Complexes
Simple Synthetic Methods
for Multinuclear Complexes Using
Various C-C Coupling Reactions
Springer Theses
Recognizing Outstanding Ph.D. Research
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Yasuomi Yamazaki
Development of Synthetic
Methods for Novel
Photofunctional Multinuclear
Complexes
Simple Synthetic Methods for Multinuclear
Complexes Using Various C-C Coupling
Reactions
Doctoral Thesis accepted by
Tokyo Institute of Technology, Tokyo, Japan
Author Supervisor
Dr.YasuomiYamazaki Prof.OsamuIshitani
DepartmentofMaterialsandLife DepartmentofChemistry
Sciences SchoolofScience
FacultyofScienceandTechnology TokyoInstituteofTechnology
SeikeiUniversity Tokyo,Japan
Tokyo,Japan
ISSN2190-5053 ISSN2190-5061 (electronic)
SpringerTheses
ISBN978-981-16-7147-0 ISBN978-981-16-7148-7 (eBook)
https://doi.org/10.1007/978-981-16-7148-7
©SpringerNatureSingaporePteLtd.2022
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Supervisor’s Foreword
Globalwarmingandthedepletionoffossilresourcesareseriousthreatstothefuture
ofhumanbeings.Thedevelopmentofusefulphotofunctionalcompoundsforsolar
energyconversionisanurgentpriorityforachievingasustainablesociety.Oneofthe
usefulstrategiesshouldbeanintegrationofdifferentmetalcomplexeswithdifferent
photofunctions, which can induce various processes such as excitation energy and
electrontransfer,andcatalyticreactions.Fromthisviewpoint,Dr.Yamazaki’sPh.D.
work has a strong impact on science and technology, especially for improving the
conversionefficiencyofsolarenergytochemicalenergy.
The thesis written by Dr. Yasuomi Yamazaki addresses new synthetic methods
for a novel class of various photofunctional multinuclear complexes. He applied
the various C-C coupling methods, which have been originally developed for the
synthesis of organic compounds, to the synthesis of photofunctional multinuclear
metal complexes. By using these synthetic methods, he successfully made various
typesofmultinuclearcomplexeswithhighphotofunctions,suchaslight-harvesting
properties and photocatalyses. For instance, he developed various photocatalysts
consistingofphotosensitizerandcatalystunits,ofwhichphotocatalyticabilitiesfor
CO reduction are much higher compared to the corresponding mixed system of
2
mononuclear complexes due to rapid intramolecular electron transfer between the
photosensitizerandcatalystunits.Light-harvestingmultinuclearcomplexesarethe
otherimportantexamples,whererapidintramolecularenergytransferaccumulates
excitationenergyintooneunit.
The main contents of the Ph.D. thesis of Dr. Yasuomi Yamazaki have already
beenpublishedin7high-levelinternationaljournalssuchasChemicalScienceand
InorganicChemistry.
Tokyo,Japan OsamuIshitani
March2021
v
ListofPublishedArticles
Partsofthisthesishavebeenpublishedinthefollowingjournalarticles:
(1) Y.Yamazaki,T.Morimoto,O.Ishitani,“SynthesisofNovelPhotofunctional
Multinuclear Complexes Using a Coupling Reaction”, Dalton Trans., 2015,
44,11626–11635.
(2) Y.Yamazaki,A.Umemoto,O.Ishitani,“PhotochemicalHydrogenationofπ-
Conjugated Bridging Ligands on Photofunctional Multinuclear Complexes”,
Inorg.Chem.,2016,55,11110–11124.
(3) Y. Yamazaki, O. Ishitani, “Selectivity control between Mizoroki-Heck and
homo-coupling reactions for synthesising multinuclear metal complexes:
unique addition effects of tertiary phosphines and O ”, Dalton Trans., 2017,
2
46,4816–4823.
(4) Y.Yamazaki,O.Ishitani,“SynthesisofOs(II)–Re(I)–Ru(II)hetero-trinuclear
complexes and their photophysical properties and photocatalytic abilities”,
Chem.Sci.,2018,9,1031–1041.
(5) Y. Yamazaki, J. Rohacova, H. Ohtsu, M. Kawano, O. Ishitani, “Synthesis of
Re(I) Rings Comprising Different Re(I) Units and Their Light-Harvesting
Abilities”,Inorg.Chem.,2018,57,15158–15171.
(6) Y.Yamazaki,O.Ishitani,“SynthesisofanEmissiveSpectacle-ShapedHexanu-
clearRhenium(I)Complex”,Inorg.Chem.,2019,58,12905–12910.
(7) Y. Yamazaki, J. Rohacova, K. Koike, O. Ishitani, “Synthesis and Light-
HarvestingFunctionsofRing-ShapedRe(I)TrinuclearComplexesConnected
withanEmissiveRu(II)Complex”,JACSAu,2021,1,294–307.
vii
Acknowledgements
Firstandforemost,Iwouldliketoexpressmysincerethankstomysupervisor,Prof.
Osamu Ishitani, for his continuous discussion, suggestions, and supports. I have
respect for his great effort in research and education. I will build on the variable
experiences in the Ishitani laboratory to work as a researcher. I look forward to
continuouscollaborationworkwithhim.
Besidesmysupervisor,IwishtothankProf.KazuhikoMaedaandProf.Tatsuki
Morimotofortheircountlessencouragementandinsightfulcommentsinthelabo-
ratorymeetings.Igratefullyacknowledgetheworkofpastandpresentmembersof
theIshitanilaboratory.
I amgrateful toProf.Masaki Kawano and Prof.HiroyoshiOhtsu forthe X-ray
crystalanalysis.IalsothankProf.HiromuKumagai,Prof.HiroyukiTakeda,Dr.Jana
Rohacova,andDr.KazuhideKoikeforthecollaborationworks.
Last,Iwouldalsoliketoexpressmygratitudetomyfamilyfortheirmoralsupport
andwarmencouragement.
March2021
ix
Contents
1 GeneralIntroduction ........................................... 1
1.1 Background ............................................... 1
1.2 OverviewofthisThesis ..................................... 4
References ..................................................... 5
2 SynthesisofMultinuclearComplexesUsingtheMizoroki–
HeckReaction ................................................. 7
2.1 Introduction ............................................... 7
2.2 ResultsandDiscussion ...................................... 8
2.2.1 Synthesis of a Re(I) Dinuclear Complex Using
theMizoroki–HeckReaction .......................... 8
2.2.2 SynthesisofVariousTrinuclearComplexesUsing
theMizoroki–HeckReaction .......................... 11
2.2.3 PhotophysicalPropertiesandPhotocatalyticAbilities
oftheTrinuclearComplexes ........................... 13
2.3 Conclusions ............................................... 21
2.4 Experimental .............................................. 22
2.4.1 GeneralProcedures ................................... 22
2.4.2 EmissionMeasurements .............................. 22
2.4.3 PhotocatalyticReactions .............................. 23
2.4.4 Materials ........................................... 23
2.4.5 Synthesis ........................................... 23
References ..................................................... 30
3 SelectiveSynthesisofVariousPhotofunctionalMultinuclear
Complexes Using a Combination of the Mizoroki–Heck
ReactionandtheHomo-couplingReaction ........................ 33
3.1 Introduction ............................................... 33
3.2 ResultsandDiscussion ...................................... 34
3.2.1 TheEffectofAirontheMizoroki–HeckReaction ........ 34
3.2.2 Concentration Effect of Phosphine Ligands
on the Reaction Abilities of the Mizoroki–Heck
Reaction ............................................ 36
xi
xii Contents
3.2.3 InvestigationoftheByproductsObservedDuring
the Mizoroki–Heck Reaction in the Absence
ofPhosphineLigands ................................. 38
3.2.4 Confirmation of the Side Reaction: Selective
Homo-couplingReactions ............................. 38
3.2.5 ParticleSizeMeasurementsofPdCompoundsDuring
theMizoroki–HeckReaction .......................... 41
3.2.6 ImprovementoftheHomo-couplingReactionUsing
MetalIndiumasanElectronDonor ..................... 42
3.2.7 StrategiesforSelectiveMizoroki–HeckReactions
andHomo-couplingReactions ......................... 44
3.2.8 SynthesisofNovelMultinuclearComplexesUsing
a Combination of the Mizoroki–Heck Reaction
andtheHomo-couplingReaction ....................... 45
3.2.9 PhotophysicalPropertiesofOsReRu .................... 48
3.3 Conclusions ............................................... 51
3.4 Experimental .............................................. 51
3.4.1 Materials ........................................... 52
3.4.2 Synthesis ........................................... 52
References ..................................................... 57
4 Photochemical and Electrochemical Hydrogenation
of π-Conjugated Bridging Ligands on Photofunctional
MultinuclearComplexes ........................................ 59
4.1 Introduction ............................................... 59
4.2 ResultsandDiscussion ...................................... 62
4.2.1 PhotochemicalHydrogenationofaVinyleneLinker
inaBridgingLigandonaRu-ReDinuclearComplex
SynthesizedbyUsingtheMizoroki–HeckReaction ....... 62
4.2.2 Purification of the Products of Photochemical
HydrogenationofRu=ReandIdentificationUsing
ESI-TOF–MS ....................................... 64
4.2.3 PhotochemicalHydrogenationwithDifferentSolvents .... 66
4.2.4 PhotochemicalHydrogenationofVariousDinuclear
Complexes with a Vinylene Linker Synthesized
byUsingtheMizoroki–HeckReaction .................. 67
4.2.5 Photochemical Hydrogenation of Dinuclear
ComplexesSynthesizedbyUsingOlefinMetathesis
andSonogashiraCoupling ............................. 70
4.2.6 Photochemical Hydrogenation with Different
WavelengthIrradiationLight .......................... 72
4.2.7 Electrochemical Hydrogenation of the Ru-Re
DinuclearComplexwithaVinyleneLinker .............. 72
4.2.8 PhotocatalyticAbilityofRu-Re-RuforCO Reduction .... 74
2