The first combined theoretical and photovoltaic characterization of both homoleptic and heteroleptic Fe(ii)-carbene sensitized photoanodes in working dye sensitized solar cells (DSSCs) has been performed. Three new heteroleptic Fe(ii)-NHC dye sensitizers have been synthesized, characterized and tested. Despite an improved interfacial charge separation in comparison to the homoleptic compounds, the heteroleptic complexes did not show boosted photovoltaic performances. The ab initio quantitative analysis of the interfacial electron and hole transfers and the measured photovoltaic data clearly evidenced fast recombination reactions for heteroleptics, even associated with un unfavorable directional electron flow, and hence slower injection rates, in the case of homoleptics. Notably, quantum mechanics calculations revealed that deprotonation of the not anchored carboxylic function in the homoleptic complex can effectively accelerate the electron injection rate and completely suppress the electron recombination to the oxidized dye. This result suggests that introduction of strong electron-donating substituents on the not-anchored carbene ligand in heteroleptic complexes, in such a way of mimicking the electronic effects of the carboxylate functionality, should yield markedly improved interfacial charge generation properties. The present results, providing for the first time a detailed understanding of the interfacial electron transfers and photovoltaic characterization in Fe(ii)-carbene sensitized solar cells, open the way to a rational molecular engineering of efficient iron-based dyes for photoelectrochemical applications.
The engineering of microbial rhodopsins with enhanced fluorescence is of great importance in the expanding field of optogenetics. Here we report the discovery of two mutants (W76S/Y179F and L83Q) of a sensory rhodopsin from the cyanobacterium Anabaena PCC7120 with opposite fluorescence behavior. In fact, while W76S/Y179F displays, with respect to the wild-type protein, a nearly tenfold increase in red-light emission, the second is not emissive. Thus, the W76S/ Y179F, L83Q pair offers an unprecedented opportunity for the investigation of fluorescence enhancement in microbial rhodopsins, which is pursued by combining transient absorption spectroscopy and multi-configurational quantum chemistry. The results of such an investigation point to an isomerization-blocking electronic effect as the direct cause of instantaneous (subpicosecond) fluorescence enhancement.
The control of ligand-field splitting in iron (II) complexes is critical to slow down the metal-to-ligand charge transfer (MLCT)-excited states deactivation pathways. The gap between the metal-centered states is maximal when the coordination sphere of the complex approaches an ideal octahedral geometry. Two new iron(II) complexes (C1 and C2), prepared from pyridylNHC and pyridylquinoline type ligands, respectively, have a near-perfect octahedral coordination of the metal. The photophysics of the complexes have been further investigated by means of ultrafast spectroscopy and TD-DFT modeling. For C1, it is shown that—despite the geometrical improvement—the excited state deactivation is faster than for the parent pseudo-octahedral C0 complex. This unexpected result is due to the increased ligand flexibility in C1 that lowers the energetic barrier for the relaxation of 3MLCT into the 3MC state. For C2, the effect of the increased ligand field is not strong enough to close the prominent deactivation channel into the metal-centered quintet state, as for other Fe-polypyridine complexes.
The development of transparent solar cells extends the applications of photovoltaics by offering the opportunity to substitute the gigantic surface coverage of windows by solar panels to produce electricity. Herein, we report a new family of NIR-sensitizers based on pyrrolopyrrole cyanine dyes, particularly efficient for the development of fully transparent and colorless dyesensitized solar cells since a record efficiency of 2.5 % was achieved with an average visible transmittance (AVT) of 76 % and a color rending index (CRI) of 93.
This paper reports an amplified spontaneous emission (ASE) initiated by intrinsically passivating grain boundary defects and aligning transition dipoles in polycrystalline perovskite (MAPbBr3) films. The method is developed by using concurrently occurring fast and slow growths to attach small grains on surfaces of large grains toward low‐threshold ASE. This materials processing utilizes one‐step solution method of mixing two MAPbBr3 precursor (PbBr2‐based and Pb(Ac)2 · 3H2O‐based) solutions to control two subsequent growths: quickly growing large grains followed by slowly growing small grains, leading to unique emitting centers from large grains and self‐doping agents from small grains. With this design, spectral narrowing phenomenon is observed from the large grains with the full width at half maximum decreasing from 21 to 4 nm when the pumping fluence is increased from 2 to 10 µW, generating an efficient ASE. Concurrently, the observed ASE shows a linear polarization reaching 21.1%, indicating that the transition dipoles in large grains are linearly polarized with coherent interaction. Therefore, this processing strategy presents a unique method to intrinsically passivate grain boundary defects and align transition dipoles toward developing ASE by attaching small grains (serving as passivation agent) to the surfaces of large grains (functioning as light‐emitting centers).
The development of transparent solar cells extends the applications of photovoltaics by offering the opportunity to substitute the gigantic surface coverage of windows by solar panels to produce electricity. Herein, we report a new family of NIR‐sensitizers based on pyrrolopyrrole cyanine dyes, particularly efficient for the development of fully transparent and colorless dye‐sensitized solar cells since a record efficiency of 2.5 % was achieved with an average visible transmittance (AVT) of 76 % and a color rending index (CRI) of 93.
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