1. |
- Andersson, Olov, 1979-, et al.
(author)
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WARA-PS : a research arena for public safety demonstrations and autonomous collaborative rescue robotics experimentation
- 2021
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In: Autonomous Intelligent Systems. - : Springer Nature. - 2730-616X. ; 1:1
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Journal article (peer-reviewed)abstract
- A research arena (WARA-PS) for sensing, data fusion, user interaction, planning and control of collaborative autonomous aerial and surface vehicles in public safety applications is presented. The objective is to demonstrate scientific discoveries and to generate new directions for future research on autonomous systems for societal challenges. The enabler is a computational infrastructure with a core system architecture for industrial and academic collaboration. This includes a control and command system together with a framework for planning and executing tasks for unmanned surface vehicles and aerial vehicles. The motivating application for the demonstration is marine search and rescue operations. A state-of-art delegation framework for the mission planning together with three specific applications is also presented. The first one concerns model predictive control for cooperative rendezvous of autonomous unmanned aerial and surface vehicles. The second project is about learning to make safe real-time decisions under uncertainty for autonomous vehicles, and the third one is on robust terrain-aided navigation through sensor fusion and virtual reality tele-operation to support a GPS-free positioning system in marine environments. The research results have been experimentally evaluated and demonstrated to industry and public sector audiences at a marine test facility. It would be most difficult to do experiments on this large scale without the WARA-PS research arena. Furthermore, these demonstrator activities have resulted in effective research dissemination with high public visibility, business impact and new research collaborations between academia and industry.
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3. |
- Chábera, Pavel, et al.
(author)
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Band-selective dynamics in charge-transfer excited iron carbene complexes
- 2019
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 216:2019, s. 191-210
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Journal article (peer-reviewed)abstract
- Ultrafast dynamics of photoinduced charge transfer processes in light-harvesting systems based on Earth-abundant transition metal complexes are of current interest for the development of molecular devices for solar energy conversion applications. A combination of ultrafast spectroscopy and first principles quantum chemical calculations of a recently synthesized iron carbene complex is used to elucidate the ultrafast excited state evolution processes in these systems with particular emphasis on investigating the underlying reasons why these complexes show promise in terms of significantly extended lifetimes of charge transfer excited states. Together, our results challenge the traditional excited state landscape for iron-based light harvesting transition metal complexes through radically different ground and excited state properties in alternative oxidation states. This includes intriguing indications of rich band-selective excited state dynamics on ultrafast timescales that are interpreted in terms of excitation energy dependence for excitations into a manifold of charge-transfer states. Some implications of the observed excited state properties and photoinduced dynamics for the utilization of iron carbene complexes for solar energy conversion applications are finally discussed.
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4. |
- Chábera, Pavel, et al.
(author)
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Photofunctionality of iron(III) N-heterocyclic carbenes and related d5 transition metal complexes
- 2021
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In: Coordination Chemistry Reviews. - : Elsevier BV. - 0010-8545. ; 426
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Research review (peer-reviewed)abstract
- Despite a few reports of photoluminescent and strongly photo-oxidizing transition metal complexes with a d5 electronic configuration, the photophysics and photochemistry of this class of transition metal complexes have largely remained unexplored. Recent investigations of earth-abundant iron(III) N-heterocyclic carbene (NHC) complexes have demonstrated promising photophysical and photochemical properties associated with low-spin (doublet) ligand-to-metal charge transfer (2LMCT) excitations, including nanosecond photoluminescence (PL) and capabilities to drive both photo-oxidation and photo-reduction reactions. These encouraging results are at first sight surprising in light of the general scarcity of known photofunctional complexes of any transition metal complexes with a d5 electronic configuration, including 1st, 2nd and 3rd row transition metal complexes of Mn(II), Tc(II), Re(II), Fe(III), Ru(III) and Os(III). Here, we review the photophysical and photochemical properties of the new Fe(III) NHC complexes together with related d5 transition metal complexes as a basis for a broader understanding of the unorthodox photophysical and photochemical properties associated with this open-shell electronic configuration. This includes considerations of the role of charge and spin effects on the ground state electronic structure, as well as discussions of charge transfer (CT) and metal centered (MC) excited state properties. The special properties of 2LMCT excited states are emphasized as a key feature to understand the photophysics of many photofunctional d5 transition metal complexes. Further aspects of excited state dynamics with d5 light-harvesting complexes, including both intra- and inter-molecular charge transfer processes, are also discussed. Finally, some fundamental challenges and emerging opportunities for further development of photofunctional Fe(III) NHC and related LMCT/d5 complexes for light-harvesting, light-emitting, and photo(electro)chemical applications are outlined. This includes some general considerations of how the specific photochemical properties of the LMCT/d5 complexes provides an exciting opportunity to develop a unique niche within the diversity of photofunctional molecular systems alongside other types of organic and inorganic chromophores commonly used in the field of molecular photochemistry.
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5. |
- Kaufhold, Simon, et al.
(author)
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Microsecond Photoluminescence and Photoreactivity of a Metal-Centered Excited State in a Hexacarbene-Co(III) Complex
- 2021
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In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; , s. 1307-1312
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Journal article (peer-reviewed)abstract
- The photofunctionality of the cobalt-hexacarbene complex [Co(III)(PhB(MeIm)3)2]+ (PhB(MeIm)3 = tris(3-methylimidazolin-2-ylidene)(phenyl)borate) has been investigated by time-resolved optical spectroscopy. The complex displays a weak (φ ∼10-4) but remarkably long-lived (τ ∼1 μs) orange photoluminescence at 690 nm in solution at room temperature following excitation with wavelengths shorter than 350 nm. The strongly red-shifted emission is assigned from the spectroscopic evidence and quantum chemical calculations as a rare case of luminescence from a metal-centered state in a 3d6 complex. Singlet oxygen quenching supports the assignment of the emitting state as a triplet metal-centered state and underlines its capability of driving excitation energy transfer processes.
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- Kjær, Kasper Skov, et al.
(author)
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Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime
- 2019
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In: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 363:6424, s. 249-253
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Journal article (peer-reviewed)abstract
- Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer (CT) states of most Fe complexes are limited by picosecond or sub-picosecond deactivation through low-lying metal centered (MC) states, resulting in inefficient electron transfer reactivity and complete lack of photoluminescence. Here we show that octahedral coordination of Fe(III) by two mono-anionic facial tris-carbene ligands can suppress such deactivation dramatically. The resulting complex [Fe(phtmeimb)2]+, where phtmeimb is [phenyl(tris(3-methylimidazol-1-ylidene))borate]-, exhibits strong, visible, room temperature photoluminescence with a 2.0 ns lifetime and 2% quantum yield via spin-allowed transition from a ligand-to-metal charge-transfer (2 LMCT) state to the ground state (2 GS). Reductive and oxidative electron transfer reactions were observed for the2 LMCT state of [Fe(phtmeimb)2]+ in bimolecular quenching studies with methylviologen and diphenylamine.
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7. |
- Kolesnichenko, Pavel V., et al.
(author)
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Viking Spectrophotometer : A Home-Built, Simple, and Cost-Efficient Absorption and Fluorescence Spectrophotometer for Education in Chemistry
- 2023
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In: Journal of Chemical Education. - : American Chemical Society (ACS). - 0021-9584 .- 1938-1328. ; 100:3, s. 1128-1137
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Journal article (peer-reviewed)abstract
- Investigating the optical properties of various chemical compounds using UV-vis spectrophotometers is an essential part of education in chemistry. However, commercial spectrophotometers are usually treated as "magic black boxes", where the dominant majority of optical elements are hidden "under the hood". This often limits understanding of the mechanisms behind the generation of spectral curves, which in turn may impede the ability to understand the limitations of the applied method and, in some cases, interpret the acquired data. In addition, the study of optical emission phenomena using fluorescence spectrophotometers is seldom implemented in educational laboratories due to the practical challenges and costs of the devices, which severely limit pedagogic access to this topic. For students to be more confident with these two basic spectroscopy techniques, we have developed a laboratory kit that provides a multifaceted learning experience. Starting with a basic exploration of an instrument assembly, it teaches, for example, such technical concepts as spectral resolution and detection sensitivity. More fundamentally, it enables deeper learning of the Beer-Lambert law and the notion of Stokes shift. The spectrophotometer is built from cost-efficient materials and is easily scalable, making it affordable for many educational laboratories. Due to a modular design, it is adaptable to various levels of education and has been successfully applied during high school-, undergraduate-, and graduate-level classes.
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8. |
- Lindh, Linnea, et al.
(author)
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Dye-sensitized solar cells based on Fe N-heterocyclic carbene photosensitizers with improved rod-like push-pull functionality
- 2021
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In: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 12:48, s. 16035-16053
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Journal article (peer-reviewed)abstract
- A new generation of octahedral iron(ii)-N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push-pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push-pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I−/I3−redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO2. Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO2. However, an ultrafast recombination process results in undesirable fast charge recombination from TiO2back to the oxidized dye, leaving only 5-10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6-8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work.
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9. |
- Lindh, Linnea, et al.
(author)
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Multifaceted Deactivation Dynamics of Fe(II) N-Heterocyclic Carbene Photosensitizers
- 2023
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In: Journal of Physical Chemistry A. - 1089-5639. ; 127:48, s. 10210-10222
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Journal article (peer-reviewed)abstract
- Excited state dynamics of three iron(II) carbene complexes that serve as prototype Earth-abundant photosensitizers were investigated by ultrafast optical spectroscopy. Significant differences in the dynamics between the investigated complexes down to femtosecond time scales are used to characterize fundamental differences in the depopulation of triplet metal-to-ligand charge-transfer (3MLCT) excited states in the presence of energetically accessible triplet metal-centered (3MC) states. Novel insights into the full deactivation cascades of the investigated complexes include evidence of the need to revise the deactivation model for a prominent iron carbene prototype complex, a refined understanding of complex 3MC dynamics, and a quantitative discrimination between activated and barrierless deactivation steps along the 3MLCT → 3MC → 1GS path. Overall, the study provides an improved understanding of photophysical limitations and opportunities for the use of iron(II)-based photosensitizers in photochemical applications.
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10. |
- Lindh, Linnea
(author)
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Photophysics and Photochemistry of Iron Carbene Complexes
- 2023
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Doctoral thesis (other academic/artistic)abstract
- Nature captures sunlight via light-absorbing molecules.Similarly, photosensitisers are used in applications of solar cells and artificial photosynthesis to absorb sunlight, and transfer the excited electron.Successful photosensitisers have in the past been based on a Ru polipyridyl scaffold, despite Ru being one of the scarcest elements in Earth's crust.This thesis work aims to replace Ru polipyridyl complexes by Fe carbene complexes, that by clever ligand design have approached suitable photosensitiser properties.One crucial property that is not yet competitive for Fe carbene photosensitisers is how long they stay in the excited state, i.e. their lifetime. This is controlled by the deactivation pathways of the molecule, dictated by the excited state landscape. Several Fe carbene photosensitisers were in this thesis investigated by spectroscopic and computational methods, to understand their deactivation pathways. For the Fe(II) carbene complexes investigated, small changes in the ligand structure influenced both what excited state (charge-transfer or metal-centred) that was mainly populated and the lifetime of the state.For the Fe(III) carbene complexes investigated, there was instead one dominating charge-transfer excited state that was rather unaffected by changes to the ligand. Furthermore, for the Fe(II) complexes metal-centred states played a large role in the deactivation pathway but for the Fe(III) complexes this was not the case.Also, one Co(III) carbene complex was investigated which displays remarkable long lifetime and emission from a metal-centred state.As a first step towards application, the electron-transfer properties of some of the photosensitisers were investigated.Fe(II) complexes with a push-pull design were able to transfer electrons to TiO2 in a solar cell configuration.The solar cell performance was however limited by an ultrafast recombination reaction, that brought a majority of the transferred electrons back to the photosensitiser.The Fe(III) complexes investigated had long enough lifetime to participate in electron transfer with other molecules in solution, if the concentration was high.Furthermore, at very high concentrations of the photosensitiser a light-induced charge-disproportionation reaction outcompeted all other deactivation pathways. In a heterogeneous catalysis configuration, this reaction could generate long-lived Fe(IV) species with the correct additives.The thesis work thus provide fundamental insights to the early implementations of Fe carbene photosensitisers in applications, by resolving key electron-transfer processes on the ultrafast timescale.
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