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Synthesis, Photophysics and Photochemistry of Uncommon Transition Metal Complexes

English title Synthesis, Photophysics and Photochemistry of Uncommon Transition Metal Complexes
Applicant Wenger Oliver
Number 156063
Funding scheme Project funding
Research institution Institut für Anorganische Chemie Universität Basel
Institution of higher education University of Basel - BS
Main discipline Inorganic Chemistry
Start/End 01.06.2015 - 31.05.2018
Approved amount 392'014.00
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Keywords (3)

coordination chemistry; water oxidation; spectroscopy

Lay Summary (German)

Lead
Metallkomplexe mit stickstoffbasierten Chelatliganden stellen eine wichtige Substanzklasse im Bereich der Photochemie und Photophysik dar. Analoge Komplexe mit phosphorbasierten Chelatliganden sind hingegen bislang im Bereich der Photochemie und Photophysik wenig untersucht worden. Ähnlich verhält es sich mit stickstoffbasierten Chelatliganden, die eine Chinon-artige Redoxchemie zeigen.
Lay summary
Im Rahmen dieses Forschungsvorhabens sollen grundlegende Aspekte der Koordinationschemie untersucht werden. Durch die Herstellung neuartiger Bindungspartner (sogenannte Liganden) sollen Metallkomplexe erhalten werden, die nützliche photochemische, photophysikalische oder elektrochemische Eigenschaften aufweisen. Von besonderem Interesse sind neue lichtemittierende Materialien sowie Katalysatoren für die lichtgetriebene Spaltung von Wasser in Wasserstoff und Sauerstoff. Zu diesem Zweck werden synthetische Methoden mit optisch-spektroskopischen und elektrochemischen Untersuchungen kombiniert.
Direct link to Lay Summary Last update: 02.10.2014

Responsible applicant and co-applicants

Employees

Publications

Publication
Luminescent Ni(0) complexes
Malzkuhn Sabine, Wenger Oliver S. (2018), Luminescent Ni(0) complexes, in Coord. Chem. Rev., 359, 52-56.
Photophysics and Photoredox Catalysis of a Homoleptic Rhenium(I) Tris(diisocyanide) Complex
Larsen Christopher B., Wenger Oliver S. (2018), Photophysics and Photoredox Catalysis of a Homoleptic Rhenium(I) Tris(diisocyanide) Complex, in Inorg. Chem., 57, 2965-2968.
A Tris(diisocyanide)chromium(0) Complex Is a Luminescent Analog of [Fe(2,2′-Bipyridine)3]2+
Büldt Laura A., Guo Xingwei, Vogel Raphael, Prescimone Alessandro, Wenger Oliver S. (2017), A Tris(diisocyanide)chromium(0) Complex Is a Luminescent Analog of [Fe(2,2′-Bipyridine)3]2+, in J. Am. Chem. Soc., 139, 985-992.
Chromium complexes for luminescence, solar cells, photoredox catalysis, upconversion, and phototriggered NO release
Büldt Laura A., Wenger Oliver S. (2017), Chromium complexes for luminescence, solar cells, photoredox catalysis, upconversion, and phototriggered NO release, in Chem. Sci., 8, 7359-7367.
Chromium(0), Molybdenum(0), and Tungsten(0) Isocyanide Complexes as Luminophores and Photosensitizers with Long-Lived Excited States
Büldt Laura A., Wenger Oliver S. (2017), Chromium(0), Molybdenum(0), and Tungsten(0) Isocyanide Complexes as Luminophores and Photosensitizers with Long-Lived Excited States, in Angew. Chem. Int. Ed., 56, 5676-5682.
Luminescent complexes made from chelating isocyanide ligands and earth-abundant metals
Büldt Laura A., Wenger Oliver S. (2017), Luminescent complexes made from chelating isocyanide ligands and earth-abundant metals, in Dalton Trans., 46, 15175-15177.
Luminescent Ni(0) Diisocyanide Chelates as Analogues of Cu(I) Diimine Complexes
Büldt Laura A., Larsen Christopher B., Wenger Oliver S. (2017), Luminescent Ni(0) Diisocyanide Chelates as Analogues of Cu(I) Diimine Complexes, in Chem. Eur. J., 23, 8577-8580.
A Molybdenum(0) Isocyanide Analogue of [Ru(2,2’-Bipyridine)3]2+: A Strong Reductant for Photoredox Catalysis
Büldt Laura A., Guo Xingwei, Prescimone Alessandro, Wenger Oliver S. (2016), A Molybdenum(0) Isocyanide Analogue of [Ru(2,2’-Bipyridine)3]2+: A Strong Reductant for Photoredox Catalysis, in Angew. Chem. Int. Ed., 55, 11247-11250.
Photoredox Properties of Homoleptic d6 Metal Complexes with the Electron-Rich 4,4',5,5'-Tetramethoxy-2,2'-bipyridine Ligand
Büldt Laura A., Prescimone Alessandro, Neuburger Markus, Wenger Oliver S. (2015), Photoredox Properties of Homoleptic d6 Metal Complexes with the Electron-Rich 4,4',5,5'-Tetramethoxy-2,2'-bipyridine Ligand, in Eur. J. Inorg. Chem., 4666-4677.

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Institutsvortrag, Université de Montréal Individual talk From Photoinduced Electron Transfer and Photoredox Catalysis to New Photosensitizers 15.03.2018 Montreal, Canada Wenger Oliver;
Institutsvortrag, École normale supérieure de Lyon Individual talk Photoinduced Electron Transfer and Luminescent Metal Complexes 31.01.2018 Lyon, France Wenger Oliver;
Institutsvortrag, Westfälische Wilhelms-Universität Münster Individual talk From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 11.01.2018 Münster, Germany Wenger Oliver;
Institutsvortrag, Friedrich-Alexander-Universität Erlangen Individual talk From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 21.12.2017 Erlangen, Germany Wenger Oliver;
Institutsvortrag, City University of Hong Kong Individual talk From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 24.11.2017 Hongkong, Hongkong Wenger Oliver;
Institutsvortrag, The Hong Kong University Individual talk From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 23.11.2017 Hongkong, Hongkong Wenger Oliver;
Institutsvortrag, Southern University of Science and Technology Individual talk From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 21.11.2017 Shenzhen, China Wenger Oliver;
URPP LightChec Symposium, University of Zurich Talk given at a conference From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 10.11.2017 Zürich, Switzerland Wenger Oliver;
Solchem, Ulm Symposium on Solar-Driven Chemistry Talk given at a conference From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 08.10.2017 Ulm, Germany Wenger Oliver;
Institutsvortrag, Université de Paris-Saclay Individual talk From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 05.10.2017 Paris-Saclay, France Wenger Oliver;
Institutsvortrag, University of Padova Individual talk From Photoinduced Electron Transfer to Charge Accumulation and New Photosensitizers 28.09.2017 Padova, Italy Wenger Oliver;
GDCh Wissenschaftsforum Talk given at a conference Photoactive Cr(0) and Mo(0) Isocyanide Complexes for Luminescence, Upconversion, and Photoredox Catalysis 10.09.2017 Berlin, Germany Büldt Laura; Wenger Oliver;
International Conference on Photochemistry Talk given at a conference Luminescent Cr(0), Mo(0) and Ni(0) Isocyanide Chelate Complexes and Their Applications 16.07.2017 Strasbourg, France Wenger Oliver;
International Symposium on Photochemistry and Photophysics of Coordination Compounds Talk given at a conference Luminescent Cr(0), Mo(0) and Ni(0) Isocyanide Chelate Complexes and Their Applications 09.07.2017 Oxford, Great Britain and Northern Ireland Wenger Oliver; Büldt Laura;
Institutsvortrag, Kyoto University Individual talk From Photoinduced Electron Transfer to Charge Accumulation and new Photosensitizers 30.06.2017 Kyoto, Japan Wenger Oliver;
Institutsvortrag, Universität Bern Individual talk From Photoinduced Electron Transfer to New Luminophores, Photocatalysis and Artificial Photosynthesis 15.06.2017 Bern, Switzerland Wenger Oliver;
Institutsvortrag, Université de Paris-Diderot Individual talk From photoinduced electron transfer to light-driven charge accumulation and new photosensitizers 20.01.2017 Paris, France Wenger Oliver;
Institutsvortrag, Université de Strasbourg Individual talk Photoinduced electron transfer with metal complexes 18.01.2017 Strasbourg, France Wenger Oliver;
Institutsvortrag, Queen Mary University of London Individual talk Photoinduced electron and proton transfer with metal complexes and organic molecules 21.10.2016 London, Great Britain and Northern Ireland Wenger Oliver;
Institutsvortrag, École nationale supérieure de chimie de Mulhouse Individual talk Photoinduced Electron Transfer with Metal Complexes and Organic Molecules 29.09.2016 Mulhouse, France Wenger Oliver;
Institutsvortrag, Georg-August-Universität Göttingen Individual talk Light-driven charge accumulation and other fundamental processes for solar energy conversion 17.05.2016 Göttingen, Germany Wenger Oliver;


Associated projects

Number Title Start Funding scheme
178760 Photoactive Metal Complexes from Earth-Abundant Elements and Multi-Electron Photochemistry in Donor-Acceptor Compounds 01.08.2018 Project funding

Abstract

2,2’-bipyridine and related alpha-diimine ligands form luminescent complexes with a variety of d6 and d8 metals, many of which are very well investigated. The phosphorous analog of 2,2’-bipyridine is called 2,2’-biphosphinine and has been known since 1991. Several transition metal complexes with 2,2’-biphosphinine have been synthesized but the photophysical and photochemical properties of these complexes have remained essentially unexplored. For well-selected complexes with bi- and tridentate phosphinine ligands there is good reason to expect similar (emissive) metal-to-ligand charge transfer (MLCT) excited states as for many alpha-diimine complexes of d6 and d8 metals. However, 2,2’-biphosphinine tends to stabilize metals in lower oxidation states than 2,2’-bipyridine, and some complexes of 2,2’-biphosphinine adopt a trigonal-prismatic geometry rather the octahedral coordination usually encountered in homoleptic 2,2’-bipyridine d6 metal complexes. In addition, 2,2’-biphosphinine is more redox non-innocent than 2,2’-bipyridine. One can therefore expect certain analogies but also some pronounced differences between the photophysics of 2,2’-biphosphinine and 2,2’-bipyridine complexes. The goal of the first part of this proposal (sub-project 1) is to synthesize new luminescent metal complexes with bi- or tridentante phosphinine ligands and to obtain a detailed fundamental understanding of their photophysical and photochemical properties. The work will not be limited to 2,2’-biphosphinine and its derivatives but will encompass bi- and tridentate chelating ligands including for example pyridylphosphinines and phenylphosphinines. This research has the potential to lead to new luminescent materials, photo- or electrocatalysts for CO2 reduction, photosensitizers for dye-sensitized solar cells, potent photooxidants for electron transfer studies in proteins, DNA intercalators, or chemical sensors for volatile organic compounds.The second part of the proposed research (sub-project 2) concentrates on novel bipyridine and terpyridine ligands which are expected to show catechol-like redox properties (Figure 2). The ultimate goal is to develop new transition metal complexes which can undergo multiple oxidations in a reversible fashion at relatively modest electrochemical potentials. Such complexes are of interest as catalysts for a variety of different multi-electron conversions including for example water oxidation or CO2 fixation. Common alpha-diimine complexes such as [Ru(2,2’-bipyridine)3]2+ exhibit simple one-electron redox chemistry, and they usually cannot undergo multi-electron reactions. The ligands in Figure 2 are expected to be highly redox-active, and when coordinated to metal complexes unusually rich multi-electron (photo)redox chemistry might result. Multiple oxidations of these complexes should be possible over a relatively small potential window due to the fact that the respective ligands can release protons upon oxidation, thereby avoiding the formation of highly charged species. Initial work will focus mostly on substitution-inert d6 metal complexes, but in the mid- to long-term more earth-abundant 3d metals will be investigated.
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