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- Chábera, Pavel, et al.
(författare)
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A low-spin Fe(iii) complex with 100-ps ligand-to-metal charge transfer photoluminescence
- 2017
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Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 543:7647, s. 695-699
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Tidskriftsartikel (refereegranskat)abstract
- Transition-metal complexes are used as photosensitizers1, in light-emitting diodes, for biosensing and in photocatalysis2. A key feature in these applications is excitation from the ground state to a charge-transfer state3,4; the long charge-transfer-state lifetimes typical for complexes of ruthenium5 and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron6 and copper7 being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs6,8,9,10, it remains a formidable scientific challenge11 to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered12 photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers13,14,15. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes4,16,17. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.
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| 2. |
- Hosseinzadeh, Griffin, et al.
(författare)
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Type Ibn Supernovae Show Photometric Homogeneity and Spectral Diversity at Maximum Light
- 2017
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Ingår i: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 836:2
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Tidskriftsartikel (refereegranskat)abstract
- Type Ibn supernovae (SNe) are a small yet intriguing class of explosions whose spectra are characterized by low-velocity helium emission lines with little to no evidence for hydrogen. The prevailing theory has been that these are the core-collapse explosions of very massive stars embedded in helium-rich circumstellar material (CSM). We report optical observations of six new SNe Ibn: PTF11rfh, PTF12ldy, iPTF14aki, iPTF15ul, SN 2015G, and iPTF15akq. This brings the sample size of such objects in the literature to 22. We also report new data, including a near-infrared spectrum, on the Type Ibn SN 2015U. In order to characterize the class as a whole, we analyze the photometric and spectroscopic properties of the full Type Ibn sample. We find that, despite the expectation that CSM interaction would generate a heterogeneous set of light curves, as seen in SNe IIn, most Type Ibn light curves are quite similar in shape, declining at rates around 0.1 mag day(-1) during the first month after maximum light, with a few significant exceptions. Early spectra of SNe Ibn come in at least two varieties, one that shows narrow P Cygni lines and another dominated by broader emission lines, both around maximum light, which may be an indication of differences in the state of the progenitor system at the time of explosion. Alternatively, the spectral diversity could arise from viewing-angle effects or merely from a lack of early spectroscopic coverage. Together, the relative light curve homogeneity and narrow spectral features suggest that the CSM consists of a spatially confined shell of helium surrounded by a less dense extended wind.
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