Photo- and redox activation of homo-and heteronuclear transition metal clusters: experiment and theory

Thesis

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Titlepage

Contents

Chapter 1 Introduction

Chapter 2 Research Methods and Instrumentation

Chapter 3 First Direct Observation and Characterization of the Lowest Excited State and Primary Photoproducts of [Ru₃(CO)₁₂] and [Os₃(CO)₁₀(1,3-cyclohexadiene)] by Picosecond Time-Resolved UV-vis and IR Spectroscopies

Chapter 4 Part A The First Steps of the Light-Induced Biradical and Zwitterion Formation from the Clusters [Os3(CO)10(α-diimine)] Studied with Ultrafast Time-Resolved UV-vis and IR Absorption Spectroscopies

Chapter 4 Part B Thermal Pathways of the Biradical Photoproducts of the Cluster [Os₃(CO)₁₀(iPr-AcPy)] Analyzed with Time-Resolved Single-Wavelength Transient Absorption Spectroscopy

Chapter 4 Part C Redox-Controlled Charge-Transfer Photochemistry of [Os₃(CO)₁₀(AcPy-MV²⁺)] (AcPy-MV²⁺= [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridin-1,1'-diium-1-yl)-ethyl)](PF6)2)

Chapter 5 Marked Influence of the Bridging Carbonyl Ligands on the Photo- and Electrochemistry of the Clusters [Ru₃(CO)₈(μ-CO)₂(α-diimine)] (α-diimine = 2,2'-bipyridine, 4,4'-dimethyl-2,2'- bipyridine and 2,2'-bipyrimidine)

Chapter 6 Multiple Evidence for Heterosite Effects in the Novel Heteronuclear Clusters [Os2Ru(CO)12-n(L)] (n = 1, L= PPh3; n = 2, L=2-acetylpyridine-N-isopropylimine)

Chapter 7 Part A Exploring the Photoreactivity of the Triangular Mixed-Metal Clusters [Os2Pt(CO)8(PPh3)2] and [Os2Rh(CO)9(η5-C5Me5)]

Chapter 7 Part B Photo- and Electrochemically Driven Conversion of the Heterometallic Cluster [Ru₃Ir(μ3-H)(CO)₁₃] into [Ru₃Ir(μ-H)₃-n(CO)₁₂]n- (n=0-2)

Summary

Samenvatting

Dankwoord

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