Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current ...interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S
, and 2 × T
with an energy difference of >5000 cm
. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result highlights the sensitivity of the electronic coupling element between the singlet and correlated triplet pair states, to the dimer conformation in dictating singlet fission efficiency even when the energetic requirements are met.
The development of non-natural photoenzymatic systems has reinvigorated the study of photoinduced electron transfer (ET) within protein active sites, providing new and unique platforms for ...understanding how biological environments affect photochemical processes. In this work, we use ultrafast spectroscopy to compare the photoinduced electron transfer in known photoenzymes. 12-Oxophytodienoate reductase 1 (OPR1) is compared to Old Yellow Enzyme 1 (OYE1) and morphinone reductase (MR). The latter enzymes are structurally homologous to OPR1. We find that slight differences in the amino acid composition of the active sites of these proteins determine their distinct electron-transfer dynamics. Our work suggests that the inside of a protein active site is a complex/heterogeneous dielectric network where genetically programmed heterogeneity near the site of biological ET can significantly affect the presence and lifetime of various intermediate states. Our work motivates additional tunability of Old Yellow Enzyme active-site reorganization energy and electron-transfer energetics that could be leveraged for photoenzymatic redox approaches.
Broadband transient absorption and two-dimensional electronic spectroscopy (2DES) studies of methylene blue in aqueous solution are reported. By isolating the coherent oscillations of the nonlinear ...signal amplitude and Fourier transforming with respect to the population time, we analyzed a significant number of coherences in the frequency domain and compared them with predictions of the vibronic spectrum from density function theory (DFT) calculations. We show here that such a comparison enables reliable assignments of vibrational coherences to particular vibrational modes, with their constituent combination bands and overtones also being identified via Franck–Condon analysis aided by DFT. Evaluation of the Fourier transform (FT) spectrum of transient absorption recorded to picosecond population times, in coincidence with 2D oscillation maps that disperse the FT spectrum into the additional excitation axis, is shown to be a complementary approach toward detailed coherence determination. Using the Franck–Condon overlap integrals determined from DFT calculations, we modeled 2D oscillation maps up to two vibrational quanta in the ground and excited state (six-level model), showing agreement with experiment. This semiquantitative analysis is used to interpret the geometry change upon photoexcitation as an expansion of the central sulfur/nitrogen containing ring due to the increased antibonding character in the excited state.
The properties of organic molecules can be influenced by magnetic fields, and these magnetic field effects are diverse. They range from inducing nuclear Zeeman splitting for structural determination ...in NMR spectroscopy to polaron Zeeman splitting organic spintronics and organic magnetoresistance. A pervasive magnetic field effect on an aromatic molecule is the aromatic ring current, which can be thought of as an induction of a circular current of π-electrons upon the application of a magnetic field perpendicular to the π-system of the molecule. While in NMR spectroscopy the effects of ring currents on the chemical shifts of nearby protons are relatively well understood, and even predictable, the consequences of these modified electronic states on the spectroscopy of molecules has remained unknown. In this work, we find that photophysical properties of model phthalocyanine compounds and their aggregates display clear magnetic field dependences up to 25 T, with the aggregates showing more drastic magnetic field sensitivities depending on the intermolecular interactions with the amplification of ring currents in stacked aggregates. These observations are consistent with ring currents measured in NMR spectroscopy and simulated in time-dependent density functional theory calculations of magnetic field-dependent phthalocyanine monomer and dimer absorption spectra. We propose that ring currents in organic semiconductors, which commonly comprise aromatic moieties, may present new opportunities for the understanding and exploitation of combined optical, electronic, and magnetic properties.
A Telecom O‑Band Emitter in Diamond Mukherjee, Sounak; Zhang, Zi-Huai; Oblinsky, Daniel G. ...
Nano letters,
04/2023, Letnik:
23, Številka:
7
Journal Article
Recenzirano
Odprti dostop
Color centers in diamond are promising platforms for quantum technologies. Most color centers in diamond discovered thus far emit in the visible or near-infrared wavelength range, which are ...incompatible with long-distance fiber communication and unfavorable for imaging in biological tissues. Here, we report the experimental observation of a new color center that emits in the telecom O-band, which we observe in silicon-doped bulk single crystal diamonds and microdiamonds. Combining absorption and photoluminescence measurements, we identify a zero-phonon line at 1221 nm and phonon replicas separated by 42 meV. Using transient absorption spectroscopy, we measure an excited state lifetime of around 270 ps and observe a long-lived baseline that may arise from intersystem crossing to another spin manifold.
Until recently, no analytical measure of many-body delocalization in open systems had been developed, yet such a measure enables characterization of how molecular excitons delocalize in ...photosynthetic light-harvesting complexes, and in turn helps us understand quantum coherent aspects of electronic energy transfer. In this paper we apply these measures to a model peripheral light-harvesting complex, LH2 from
Rhodopseudomonas acidophila
. We find how many chromophores collectively contribute to the "delocalization length" of an excitation within LH2 and how the coherent delocalization is distributed spatially. We also investigate to what extent this delocalization length is effective, by examining the impact of bipartite and multipartite entanglement in inter-ring energy transfer in LH2.
Delocalization of a model light-harvesting complex is investigated using multipartite measures inspired by quantum information science.
We have synthesized and thoroughly characterized two representative ladder-type acetylene-bridged perylenediimide dimers bearing long alkyl chain solubilizing groups, ...bis1-ethynyl-N,N′-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide (PDICC2, 1) and 1,1′-ethynyl-bisN,N′-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide (PDI2CC, 2). In these dimeric PDI molecules, NMR-based structural characterization became nontrivial because severe 1H spectral broadening and greater than expected numbers of observed 13C resonances substantially complicated the interpretation of traditional 1-D spectra. However, rational two-dimensional NMR approaches based on both homo- and heteronuclear couplings (1H–1H COSY; 1H–13C HSQC), in conjunction with high-level structural DFT calculations (GIAO/B3LYP/6-31G(d,p)/PCM, chloroform), were readily applied to these structures, producing well-defined analytical characterization, and the associated methodology is described in detail. Furthermore, on the basis of dynamic NMR experiments, both 1 and 2 were found to exist in a perylene-centered conformational dynamic equilibrium (ΔG‡ = 13–17 kcal/mol), which primarily caused the observed ambiguities in conventional 1-D spectra.
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•A perylenediimide dimer was synthesized as a model excitonic system.•The dimer absorption spectrum reveals delocalized molecular exciton transitions.•Exciton states were not found to ...exhibit long-lived coherences.•Population transfer between the two exciton states was found to occur in <50fs.
Reports of long-lived exciton coherences have lead researchers to expect that model dimer systems inevitably generate exciton superposition states observable by two-dimensional electronic spectroscopy. Here we report a careful photophysical characterization of a model dimer system, a diacetylene-linked perylenediimide dimer to examine that issue. The absorption spectrum of the dimer shows molecular exciton splitting, indicating that excitation is delocalized. The assignment of exciton states was supported by other photophysical measurements as well as theoretical calculations. Ultrafast two-dimensional electronic spectroscopy was employed to identify and characterize excitonic and vibrational features, as they evolve over time. Population transfer between the two exciton states is found to happen in <50fs, thus preventing the sustainment of exciton coherences. We show that such fast radiationless relaxation cannot be explained by coupling to a solvent spectral density and is therefore missed by standard approaches such as Redfield theory and the hierarchical equations of motion.
Biliproteins are a unique class of photosynthetic proteins in their diverse, and at times, divergent biophysical function. The two contexts of photosynthetic light harvesting and photoreception ...demonstrate characteristically opposite criteria for success, with light harvesting demanding structurally-rigid chromophores which minimize excitation quenching, and photoreception requiring structural flexibility to enable conformational isomerization. The functional plasticity borne out in these two biological contexts is a consequence of the structural plasticity of the pigments utilized by biliproteins-linear tetrapyrroles, or bilins. In this work, the intrinsic flexibility of the bilin framework is investigated in a bottom-up fashion by reducing the active nuclear degrees of freedom through model dipyrrole subunits of the bilin core and terminus free of external protein interactions. Steady-state spectroscopy was carried out on the dipyrrole (DPY) and dipyrrinone (DPN) subunits free in solution to characterize their intrinsic spectroscopic properties including absorption strengths and nonradiative activity. Transient absorption (TA) spectroscopy was utilized to determine the mechanism and kinetics of nonradiative decay of the dipyrrole subunits, revealing dynamics dominated by rapid internal conversion with some
→
isomerization observable in DPY. Computational analysis of the ground state conformational landscapes indicates enhanced complexity in the asymmetric terminal subunit, and the prediction was confirmed by heterogeneity of species and kinetics observed in TA. Taken together, the large oscillator strengths (
∼ 0.6) of the dipyrrolic derivatives and chemically-efficient spectral tunability seen through the ∼100 nm difference in absorption spectra, validate Nature's "selection" of multi-pyrrole pigments for light capture applications. However, the rapid deactivation of the excited state via their natural torsional activity when free in solution would limit their effective biological function. Comparison with phytochrome and phycocyanin 645 crystal structures reveals binding motifs within the
bilin environment that help to facilitate or inhibit specific inter-pyrrole twisting vital for protein operation.
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