| 1. |
- Johnson, Catherine, et al.
(författare)
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Ferrous and ferric complexes with cyclometalating N-heterocyclic carbene ligands : a case of dual emission revisited
- 2023
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Ingår i: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 14:37, s. 10129-10139
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Tidskriftsartikel (refereegranskat)abstract
- Iron N-heterocyclic carbene (FeNHC) complexes with long-lived charge transfer states are emerging as a promising class of photoactive materials. We have synthesized [Fe-II(ImP)(2)] (ImP = bis(2,6-bis(3-methylimidazol-2-ylidene-1-yl)phenylene)) that combines carbene ligands with cyclometalation for additionally improved ligand field strength. The 9 ps lifetime of its (MLCT)-M-3 (metal-to-ligand charge transfer) state however reveals no benefit from cyclometalation compared to Fe(II) complexes with NHC/pyridine or pure NHC ligand sets. In acetonitrile solution, the Fe(II) complex forms a photoproduct that features emission characteristics (450 nm, 5.1 ns) that were previously attributed to a higher ((MLCT)-M-2) state of its Fe(III) analogue [Fe-III(ImP)(2)](+), which led to a claim of dual (MLCT and LMCT) emission. Revisiting the photophysics of [Fe-III(ImP)(2)](+), we confirmed however that higher ((MLCT)-M-2) states of [Fe-III(ImP)(2)](+) are short-lived (<10 ps) and therefore, in contrast to the previous interpretation, cannot give rise to emission on the nanosecond timescale. Accordingly, pristine [Fe-III(ImP)(2)](+) prepared by us only shows red emission from its lower (LMCT)-L-2 state (740 nm, 240 ps). The long-lived, higher energy emission previously reported for [Fe-III(ImP)(2)](+) is instead attributed to an impurity, most probably a photoproduct of the Fe(II) precursor. The previously reported emission quenching on the nanosecond time scale hence does not support any excited state reactivity of [Fe-III(ImP)(2)](+) itself.
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| 2. |
- Prakash, Om, et al.
(författare)
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Photophysical Integrity of the Iron(III) Scorpionate Framework in Iron(III)-NHC Complexes with Long-Lived 2LMCT Excited States
- 2022
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 61:44, s. 17515-17526
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Tidskriftsartikel (refereegranskat)abstract
- Fe(III) complexes with N-heterocyclic carbene (NHC) ligands belong to the rare examples of Earth-abundant transition metal complexes with long-lived luminescent charge-transfer excited states that enable applications as photosensitizers for charge separation reactions. We report three new hexa-NHC complexes of this class: [Fe(brphtmeimb)2]PF6 (brphtmeimb = [(4-bromophenyl)tris(3-methylimidazol-2-ylidene)borate]–, [Fe(meophtmeimb)2]PF6 (meophtmeimb = [(4-methoxyphenyl)tris(3-methylimidazol-2-ylidene)borate]–, and [Fe(coohphtmeimb)2]PF6 (coohphtmeimb = [(4-carboxyphenyl)tris(3-methylimidazol-2-ylidene)borate]–. These were derived from the parent complex [Fe(phtmeimb)2]PF6 (phtmeimb = [phenyltris(3-methylimidazol-2-ylidene)borate]– by modification with electron-withdrawing and electron-donating substituents, respectively, at the 4-phenyl position of the ligand framework. All three Fe(III) hexa-NHC complexes were characterized by NMR spectroscopy, high-resolution mass spectroscopy, elemental analysis, single crystal X-ray diffraction analysis, electrochemistry, Mößbauer spectroscopy, electronic spectroscopy, magnetic susceptibility measurements, and quantum chemical calculations. Their ligand-to-metal charge-transfer (2LMCT) excited states feature nanosecond lifetimes (1.6–1.7 ns) and sizable emission quantum yields (1.7–1.9%) through spin-allowed transition to the doublet ground state (2GS), completely in line with the parent complex [Fe(phtmeimb)2]PF6 (2.0 ns and 2.1%). The integrity of the favorable excited state characteristics upon substitution of the ligand framework demonstrates the robustness of the scorpionate motif that tolerates modifications in the 4-phenyl position for applications such as the attachment in molecular or hybrid assemblies.
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| 3. |
- de Groot, Lisa H.M., et al.
(författare)
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Iron Photoredox Catalysis-Past, Present, and Future
- 2023
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Ingår i: Journal of the American Chemical Society. - 0002-7863. ; 145:17, s. 9369-9388
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Forskningsöversikt (refereegranskat)abstract
- Photoredox catalysis of organic reactions driven by iron has attracted substantial attention throughout recent years, due to potential environmental and economic benefits. In this Perspective, three major strategies were identified that have been employed to date to achieve reactivities comparable to the successful noble metal photoredox catalysis: (1) Direct replacement of a noble metal center by iron in archetypal polypyridyl complexes, resulting in a metal-centered photofunctional state. (2) In situ generation of photoactive complexes by substrate coordination where the reactions are driven via intramolecular electron transfer involving charge-transfer states, for example, through visible-light-induced homolysis. (3) Improving the excited-state lifetimes and redox potentials of the charge-transfer states of iron complexes through new ligand design. We seek to give an overview and evaluation of recent developments in this rapidly growing field and, at the same time, provide an outlook on the future of iron-based photoredox catalysis.
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| 4. |
- Ilic, Aleksandra, et al.
(författare)
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Photoredox catalysis via consecutive 2LMCT- and 3MLCT-excitation of an Fe(iii/ii)–N-heterocyclic carbene complex
- 2022
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Ingår i: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 13:32, s. 9165-9175
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Tidskriftsartikel (refereegranskat)abstract
- Fe-N-heterocyclic carbene (NHC) complexes attract increasing attention as photosensitisers and photoredox catalysts. Such applications generally rely on sufficiently long excited state lifetimes and efficient bimolecular quenching, which leads to there being few examples of successful usage of Fe-NHC complexes to date. Here, we have employed [Fe(iii)(btz)(3)](3+) (btz = (3,3 '-dimethyl-1,1 '-bis(p-tolyl)-4,4 '-bis(1,2,3-triazol-5-ylidene))) in the addition of alkyl halides to alkenes and alkynes via visible light-mediated atom transfer radical addition (ATRA). Unlike other Fe-NHC complexes, [Fe(iii/ii)(btz)(3)](3+/2+) benefits from sizable charge transfer excited state lifetimes >= 0.1 ns in both oxidation states, and the Fe(iii) (LMCT)-L-2 and Fe(ii) (MLCT)-M-3 states are strong oxidants and reductants, respectively. The combined reactivity of both excited states enables efficient one-electron reduction of the alkyl halide substrate under green light irradiation. The two-photon mechanism proceeds via reductive quenching of the Fe(iii) (LMCT)-L-2 state by a sacrificial electron donor and subsequent excitation of the Fe(ii) product to its highly reducing (MLCT)-M-3 state. This route is shown to be more efficient than the alternative, where oxidative quenching of the less reducing Fe(iii) (LMCT)-L-2 state by the alkyl halide drives the reaction, in the absence of a sacrificial electron donor.
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| 5. |
- Lagou, Vasiliki, et al.
(författare)
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Sex-dimorphic genetic effects and novel loci for fasting glucose and insulin variability
- 2021
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Ingår i: Nature Communications. - : Nature Publishing Group. - 2041-1723. ; 12:1
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Tidskriftsartikel (refereegranskat)abstract
- Differences between sexes contribute to variation in the levels of fasting glucose and insulin. Epidemiological studies established a higher prevalence of impaired fasting glucose in men and impaired glucose tolerance in women, however, the genetic component underlying this phenomenon is not established. We assess sex-dimorphic (73,089/50,404 women and 67,506/47,806 men) and sex-combined (151,188/105,056 individuals) fasting glucose/fasting insulin genetic effects via genome-wide association study meta-analyses in individuals of European descent without diabetes. Here we report sex dimorphism in allelic effects on fasting insulin at IRS1 and ZNF12 loci, the latter showing higher RNA expression in whole blood in women compared to men. We also observe sex-homogeneous effects on fasting glucose at seven novel loci. Fasting insulin in women shows stronger genetic correlations than in men with waist-to-hip ratio and anorexia nervosa. Furthermore, waist-to-hip ratio is causally related to insulin resistance in women, but not in men. These results position dissection of metabolic and glycemic health sex dimorphism as a steppingstone for understanding differences in genetic effects between women and men in related phenotypes.
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| 6. |
- Locke, Adam E, et al.
(författare)
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Genetic studies of body mass index yield new insights for obesity biology.
- 2015
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Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 518:7538, s. 197-401
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Tidskriftsartikel (refereegranskat)abstract
- Obesity is heritable and predisposes to many diseases. To understand the genetic basis of obesity better, here we conduct a genome-wide association study and Metabochip meta-analysis of body mass index (BMI), a measure commonly used to define obesity and assess adiposity, in up to 339,224 individuals. This analysis identifies 97 BMI-associated loci (P < 5 × 10(-8)), 56 of which are novel. Five loci demonstrate clear evidence of several independent association signals, and many loci have significant effects on other metabolic phenotypes. The 97 loci account for ∼2.7% of BMI variation, and genome-wide estimates suggest that common variation accounts for >20% of BMI variation. Pathway analyses provide strong support for a role of the central nervous system in obesity susceptibility and implicate new genes and pathways, including those related to synaptic function, glutamate signalling, insulin secretion/action, energy metabolism, lipid biology and adipogenesis.
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| 7. |
- Moberg, Christina, et al.
(författare)
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De unga gör helt rätt när de stämmer staten
- 2022
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Ingår i: Aftonbladet. - 1103-9000.
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Tidskriftsartikel (populärvet., debatt m.m.)abstract
- 1 620 forskare och lärare i forskarvärlden: Vi ställer oss bakom Auroras klimatkrav
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| 8. |
- Rosemann, Nils W., et al.
(författare)
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Competing dynamics of intramolecular deactivation and bimolecular charge transfer processes in luminescent Fe(iii) N-heterocyclic carbene complexes
- 2023
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Ingår i: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 14:13, s. 3569-3579
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Tidskriftsartikel (refereegranskat)abstract
- Steady state and ultrafast spectroscopy on [FeIII(phtmeimb)2]PF6 (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate) was performed over a broad range of temperatures. The intramolecular deactivation dynamics of the luminescent doublet ligand-to-metal charge-transfer (2LMCT) state was established based on Arrhenius analysis, indicating the direct deactivation of the 2LMCT state to the doublet ground state as a key limitation to the lifetime. In selected solvent environments photoinduced disproportionation generating short-lived Fe(iv) and Fe(ii) complex pairs that subsequently undergo bimolecular recombination was observed. The forward charge separation process is found to be temperature-independent with a rate of ∼1 ps−1. Subsequent charge recombination takes place in the inverted Marcus region with an effective barrier of 60 meV (483 cm−1). Overall, the photoinduced intermolecular charge separation efficiently outcompetes the intramolecular deactivation over a broad range of temperatures, highlighting the potential of [FeIII(phtmeimb)2]PF6 to perform photocatalytic bimolecular reactions.
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| 9. |
- Schwarz, Jesper, et al.
(författare)
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High turnover photocatalytic hydrogen formation with an Fe(iii) N-heterocyclic carbene photosensitiser
- 2022
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; 58:35, s. 5351-5354
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Tidskriftsartikel (refereegranskat)abstract
- Herein we report the first high turnover photocatalytic hydrogen formation reaction based on an earth-abundant Fe-III-NHC photosensitiser. The reaction occurs via reductive quenching of the (LMCT)-L-2 excited state that can be directly excited with green light and employs either Pt-colloids or [Co(dmgH)(2)pyCl] as proton reduction catalysts and [HNEt3][BF4] and triethanolamine/triethylamine as proton and electron donors. The outstanding photostability of the Fe-III-NHC complex enables turnover numbers >1000 without degradation.
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| 10. |
- Schwarz, Jesper, et al.
(författare)
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Simultaneous non-invasive gas analysis in artificial photosynthesis reactions using rotational Raman spectroscopy
- 2022
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Ingår i: Sustainable Energy and Fuels. - : Royal Society of Chemistry (RSC). - 2398-4902. ; 6:19, s. 4388-4392
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Tidskriftsartikel (refereegranskat)abstract
- Optimising reactions in artificial photosynthesis research requires screening of many reaction and operation parameters, which is often resource-intense and time-consuming. In this paper, we demonstrate the use of a rotational Raman-based spectrometer for non-invasive quantification of several gases (H2, O2, N2, CO, CO2) with short analysis times (15 s), enabling high throughput screening. Furthermore, with this device, reaction progress can be monitored in situ, by real-time simultaneous quantification of multiple gases. We have applied this instrument and developed a method to study the O2 dependency of a prototypic light-driven hydrogen evolution reaction, showcasing the value of this approach for the artificial photosynthesis community in general.
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