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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Structural, Electronic, and Photophysical Insights into a Few Atom Copper-Sulfur Cluster in the Solid and Solution States

Coinage-metal chalcogenide clusters are widely studied for their attractive photoluminescence properties. Copper chalcogenides are especially promising, but are often confined to solid-state investigations due to their limited solution stability and the difficulty of synthesizing stable, well-defined clusters. Here, we investigate copper–sulfur clusters incorporating a small number of Cu atoms to elucidate fundamental atomic interactions, ground- and excited-state characteristics, and photophysical behavior in both solid and solution. We have synthesized the Cu6(4,6-dimethyl-2-mercaptopyrimidine)6 cluster in both neutral and charged states, Cu6 and Cu6-2H2+, respectively, by selective ligand protonation. The molecular structures are determined using single-crystal X-ray diffraction, while Cu K-edge X-ray absorption spectroscopy is used to probe Cu electronic structure differences arising from the ligand modification. Steady-state and pump-probe optical spectroscopy is used to investigate photophysical properties, interpreted using density functional theory methods. Both clusters exhibit good stability in the solid state and in solution and show characteristic near-infrared emission with microsecond lifetimes. Overall, the Cu6S6 clusters display favorable charge–transfer characteristics and show potential for further use in driving photochemical transformations.

Copper-sulfur clusters↗
DOE OSTI2020

Observation of the molecular response to light upon photoexcitation

Abstract When a molecule interacts with light, its electrons can absorb energy from the electromagnetic field by rapidly rearranging their positions. This constitutes the first step of photochemical and photophysical processes that include primary events in human vision and photosynthesis. Here, we report the direct measurement of the initial redistribution of electron density when the molecule 1,3-cyclohexadiene (CHD) is optically excited. Our experiments exploit the intense, ultrashort hard x-ray pulses of the Linac Coherent Light Source (LCLS) to map the change in electron density using ultrafast x-ray scattering. The nature of the excited electronic state is identified with excellent spatial resolution and in good agreement with theoretical predictions. The excited state electron density distributions are thus amenable to direct experimental observation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Simplifying the Chemical Design of Nonfused-Ring Electron Acceptors─Lessons Learned from Thienothiophene and Benzodithiophene Cores

Nonfused-ring electron acceptors (NFREA)s have been proposed as alternatives to fused-ring acceptors in organic photovoltaics (OPV)s. The simpler molecular design of NFREAs results in a reduced synthetic complexity, potentially lowering manufacturing costs, and easier access to desired optoelectronic properties by structural modifications. However, they have not seen the same rise in popularity as fused nonfullerene acceptors (NFA)s due to their lower performances in devices. In this work, we explore structure–property relationships of three NFREA molecules based on thieno[3,2-b]thiophene (TT) and benzo[1,2-b:4,5-b′]dithiophene (BDT) cores and malononitrile functionalized-isatin end group acceptors. We describe their synthetic routes, computational analysis, and photophysical and electronic properties. Here, we investigated the effect of changing the core from TT to BDT on electronic properties of the molecules─a result of raising/lowering of the frontier molecular orbital (FMO) levels. We also explored the effect of branched vs nonbranched alkyl groups on the morphological and blend-capabilities in bulk heterojunction (BHJ) OPV devices. These effects were then reflected in the overall device performances, primarily due to favorable FMO energy alignment between the NFREA and polymer. To investigate the behavior of the excited states of the NFREAs within the active layer of the devices, we performed time-resolved microwave conductivity and transient absorption experiments, which confirmed that the TT molecules exhibited very low conductance while the BDT molecule showed moderate photoconductance. Our combined theoretical, synthetic, device, and charge carrier dynamics studies of these materials reveal the central role that structure–property relationships play in future molecular designs of NFREAs that can perform as well as their fused counterparts.

14 SOLAR ENERGY↗
DOE OSTI2025

Optical Waveguiding Charge-Transfer Cocrystals: Examining the Impact of Molecular Rotations on Their Photoluminescence

Here, we present the first example of a binary optical waveguiding (OWG) cocrystal with large anisotropy featuring a fluorinated acceptor molecule (CPP-TFPN, 1) with on-plane rotational dynamics, confirmed by solid-state NMR ( 19 F T 1 ) and theoretical calculations. Spatially resolved microphotoluminescence and variable-temperature photoluminescence experiments allowed us to examine the OWG performance and photophysical properties of both single crystals and bulk microcrystalline samples. A comparison with an analogous cocrystal containing a regioisomeric acceptor (CPP-TFTN, 2) revealed that the photoluminescence characteristics of 1 are associated with the rotational motions of the acceptor, offering insights into how the molecular motion changes this property.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Photochemically Triggered Para-Hydrogen-Induced Polarization in a Diplatinum Trihydride Complex

Transition metal complexes containing platinum(II) are of substantial interest for their rich photophysics, biomedical applications, and catalytic function. Nuclear magnetic resonance (NMR) spectra of the spin-1/2 isotope, 195Pt, offer detailed insights into the molecular structures of closed-shell Pt(II) complexes, including solvent effects. However, the sensitivity of 195Pt NMR is mediocre, and its NMR spectra are typically complex. As a result, 1H NMR spectra are used as the primary characterization tool for Pt(II)-based molecules, relying on J-coupling to the 195Pt nucleus to provide structural information from the resulting satellite peaks. In efforts to significantly improve the information content from 1H NMR spectroscopy in a Pt(II)-containing molecule, we utilize [Pt2H2(μ-H)(μ-dppm)2]PF6, where dppm is bis(diphenylphosphino)methane, and leverage its established photoactivity with UV light and H2 for para-hydrogen-induced polarization (PHIP) to enhance the resultant NMR signals, revealing numerous 195Pt J-couplings. Moreover, we investigate direct solvent hyperpolarization effects, as well as the indirect effects of solvent on the various observed J-coupling constants in the Pt species, demonstrating correlations with both Lewis basicity and dielectric constant.

Brown, Emily E. [Department of Chemistry; North Ca↗
DOE OSTI2020

An activatable NIR fluorescent rosol for selectively imaging nitroreductase activity

Hypoxia (i.e., pO 2 ≤ ~1.5 %) is an important characteristic of tumor microenvironments that directly correlates with resistance against first-line therapies and tumor proliferation/infiltration. The ability to accurately identify hypoxic tumor cells/tissue could afford tailored therapeutic regimens for personalized treatment, the development of more-effective therapies, and discerning the mechanisms underlying disease progression. Fluorogenic constructs currently developed for identifying such tumor cells/tissue operate by targeting the bioreductive activity of primarily the nitroreductase (NTR) class of enzymes, but collectively such constructs unfortunately present photophysical and/or physicochemical shortcomings that could limit their effectiveness upon implementation. To overcome these limitations, we present the rational design, development, and evaluation of the first activatable ultracompact xanthene core-based molecular probe (NO 2 -Rosol) for selectively imaging NTR activity that affords an “OFF-ON” near-infrared (NIR) fluorescence response (ca. > 700 nm) alongside a remarkable Stokes shift (ca. > 150 nm) via NTR activity-facilitated modulation to its energetics whereby the resultant interplay discontinues an intramolecular d-PET fluorescence-quenching mechanism transpiring between directly-linked electronically-uncoupled π-systems comprising its components. DFT calculations guided selection of a suitable fluorogenic scaffold and nitroaromatic moiety candidate that when adjoined could (i) afford such photophysical response upon bioreduction by upregulated NTR activity in hypoxic tumor cells/tissue and (ii) employ a retention mechanism strategy that capitalizes on an inherent physical property of the NIR fluorogenic scaffold for achieving signal amplification. NO 2 -Rosol demonstrated 705 nm NIR fluorescence emission and a 157 nm Stokes shift, selectivity for NTR over relevant bioanalytes, and a 28- and 12-fold fluorescence enhancement in solution and between cells cultured under different oxic conditions, respectively. Finally, in establishing feasibility for NO 2 -Rosol to provide favorable contrast levels in in solutioand in vitrostudies, we anticipate NO 2 -Rosol similarly doing so in future studies towards its translation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Superradiance and Directional Exciton Migration in Metal–Organic Frameworks

Crystalline metal–organic frameworks (MOFs) are promising synthetic analogues of photosynthetic light-harvesting complexes (LHCs). The precise assembly of linkers (organic chromophores) around the topology-defined pores offers the evolution of unique photophysical behaviors that are reminiscence of LHCs. These include MOF excited states with photoabsorbed energy that is spatially dispersed over multiple linkers defining the molecular excitons. The multilinker molecular excitons display superradiance–a hallmark of coupled oscillators seen in LHCs–with radiative rate constant (k rad ) exceeding that of a single linker. Our theoretical model and experimental results on three zirconium MOFs, namely, PCN-222(Zn), NU-1000, and SIU-100, with similar topology but varying linkers suggest that the size of such molecular excitons depends on the electronic symmetry of the linker. This multilinker exciton model effectively predicts the energy transfer rate constant; corresponding single-step exciton hopping time, ranging from a few picoseconds in SIU-100 and NU-1000 to a few hundreds of picoseconds in PCN-222(Zn), matches well with the experimental data. The model also predicts the anisotropy of exciton displacement with preferential migration along the crystallographic c-axis. Overall, these findings establish various missing links defining the exciton size and dynamics in MOF-assembled linkers. Furthermore, the understandings will provide design principles, especially, positioning the catalysts or electrode relative to the linker orientation for low-density solar energy conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Final Technical Report

The capture of CO2 and its simultaneously conversion to useful chemical fuels driven by solar energy represents one of the best solutions to resolve our growing energy and environmental concerns. The most critical challenge to this endeavor is the rational design of a photocatalytic architecture that can effectively couple a given photosensitizer (PS) with an appropriate catalyst, thereby enabling efficient photosensitization of a multi-electron reduction catalysis. This research program aims to address this challenge using an interdisciplinary approach that combines innovative material design and synthesis, fundamental mechanistic studies, and photocatalytic performance evaluation. The strategies include 1) constructing and investigating a novel class of 2D COF hybrid photocatalysts with an effective photoactive organic building block as PS and a precisely incorporated CO2 reduction molecular catalyst (MC); and 2) mechanistic origins of CO2 photoreduction using a set of complementary time-resolved and in situ spectroscopic techniques. The novelty of the proposed hybrid system lies in the unprecedented combination of the unique advantage of porous crystalline COF PS with the precise catalytic function of MC for photocatalytic CO2 reduction. In the periods of the support (09/01/2019-12/31/2022), we have made research progress in four projects: 1) Exploring 2D COFs with incorporated Mn complex for light driven CO2 reduction; 2) The dependence of excited state and charge transfer dynamics on monomer structure of 2D COFs; and 3) Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO2 Photoreduction; and 4) The impact of monomer structure on the photoluminescence properties of COFs. We found that both monomer structure and linker chemistry can effectively impact the excited state dynamics, charge transfer properties, and photoluminescence quantum yields, the important properties that dictate their applications in photocatalysis. In addition, we found that the direction of imine linker determines charge transfer direction and thus controls the types of catalytic reactions (e.g. water oxidation or CO2 reduction reactions). The result from these fundamental studies provides important information for correlating the structure of the COF photocatalysts with their photophysical properties and catalytic functions, paving the way for their novel application in photocatalysis. We expect that our findings will contribute to addressing current shortcomings of semiconductor- and molecular-based photocatalytic systems that suffer from inefficient light harvesting and charge separation and poor adsorption and activation of reactants. In turn, this research will contribute towards the development of novel photocatalytic systems for CO2 reduction to generate renewable chemical fuels and simultaneously address the problem of mitigating climate change due to CO2 accumulation. In addition, the experimental approaches employed in this research can be easily transferred to other energy technologies and are expected to broadly impact fields involving photocatalysis, optoelectronic devices, and solar energy conversion. The proposed research has also been integrated with educational activities and serve as a basis to raise awareness around the critical issues of global energy production and consumption, and to develop the next generation of solar energy scientists.

14 SOLAR ENERGY↗
DOE OSTI2023

Sterically Encumbered Heteroleptic Copper(I) β-Diketiminate Complexes with Extended Excited-State Lifetimes

One of the main challenges in developing effective copper(I) photosensitizers is their short excited-state lifetimes, usually attributed to structural distortion upon light excitation. We have previously introduced copper(I) charge-transfer chromophores of the general formula Cu(N^N)(ArNacNac), where N^N is a conjugated diimine ligand and ArNacNac is a substituted β-diketiminate ligand. These chromophores were promising regarding their tunable redox potentials and intense visible absorption but were ineffective as photosensitizers, presumably due to short excited-state lifetimes. Here, we introduce sterically crowded analogues of these heteroleptic chromophores with bulky alkyl substituents on the N^N and/or ArNacNac ligand. Structural analysis was combined with electrochemical and photophysical characterization, including ultrafast transient absorption (UFTA) spectroscopy to investigate the effects of the alkyl groups on the excited-state lifetimes of the complexes. The molecular structures determined by single-crystal X-ray diffraction display more distortion in the ground state as alkyl substituents are introduced into the phenanthroline or the NacNac ligand, showing smaller τ 4 values due to the steric hindrance. UFTA measurements were carried out to determine the excited-state dynamics. Sterically encumbered Cu5 and Cu6 display excited-state lifetimes 15–20 times longer than unsubstituted complex Cu1, likely indicating that the incorporation of bulky alkyl substituents inhibits the pseudo-Jahn–Teller (PJT) flattening distortion in the excited state. Furthermore, this work suggests that the steric properties of these heteroleptic copper(I) charge-transfer chromophores can be readily modified and that the excited-state dynamics are strongly responsive to these modifications.

14 SOLAR ENERGY↗
DOE OSTI2024

Influence of substituents on the vectorial difference static dipole upon excitation in synthetic bacteriochlorins

Organic dye aggregates have been shown to exhibit exciton delocalization in natural and synthetic systems. Such dye aggregates show promise in the emerging area of quantum information science (QIS). We believe that the difference static dipole (Δd) is an essential dye parameter in the development of molecular QIS systems. However, a foundational understanding of the structural factors influencing Δd remains elusive. Bacteriochlorins play a vital role in photosynthesis due to their exceptional photophysical properties. Therefore, bacteriochlorins are particularly suitable dyes for the construction of aggregate systems for QIS. Synthetic bacteriochlorins further offer stability and tunability via chemical modifications. Here, the influence of substituents on the Δd of monomeric (non-aggregated) dyes was investigated via density functional theory (DFT) and time-dependent (TD-)DFT in a set of 5-methoxybacteriochlorins progressively substituted with ethynyl, phenyl, and phenylethynyl substituents at the 3,13- and 3,13,15-positions of the macrocycle. Symmetrically substituted 5-methoxybacteriochlorins were shown to have the largest Δd. The increase in Δd in the series of dyes was largely due to changes in orientation of the static dipole upon excitation rather than large changes in magnitude. In addition, the transition dipole (μ) and the angle between Δd and μ (ζ) were calculated. Three 5-methoxybacteriochlorins with high predicted Δd and μ were synthesized and characterized spectroscopically. The trend in Δd values empirically determined using the solvatochromic Stokes shift method was comparable with the DFT calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Giant Concentric Metallosupramolecule with Aggregation-Induced Phosphorescent Emission

Fluorescent metallo-supramolecules have received considerable attention due to their precisely-controlled dimensions as well as the tunable photophysical and photochemical properties. However, phosphorescent analogues are still rare, and limited to small structures with low-temperature phosphorescence. In this work, we report the self-assembly and photophysical studies of a giant, discrete metallo-supramolecular concentric hexagon functionalized with six alkynylplatinum(II) bzimpy moieties. With a size larger than 10 nm and molecular weight higher than 26,000 Da, the assembled terpyridine-based supramolecule displayed phosphorescent emission at room temperature. Moreover, the supramolecule exhibited enhanced aggregation-induced phosphorescent emission compared to the ligand by tuning the aggregation states through intermolecular interactions, and significant enhancement of emission to CO 2 gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The fluorescence quantum yield parameter in Förster resonance energy transfer (FRET)—Meaning, misperception, and molecular design

The fluorescence quantum yield parameter in Förster resonance energy transfer (FRET) processes underpins vital phenomena ranging from light harvesting in photosynthesis to design of sensors for monitoring physiological processes. The criteria for choosing a donor for use in FRET processes include chemical features (solubility, bioconjugatability, synthetic accessibility, and stability) as well as photophysical properties pertaining to absorption (wavelength and molar absorption coefficient) and fluorescence (wavelength and fluorescence quantum yield). The value of the donor fluorescence quantum yield (Φf, or emphatically, Φf(D)) alone has sometimes been thought (erroneously) to place a ceiling on the possible quantum yield of energy transfer (Φtrans). A high value of the donor Φf, while attractive, is not at all essential; indeed, many valuable candidates for use as FRET donors have likely been excluded on the basis of this injudiciously applied filter. Such disregard is unwarranted. In this tutorial overview, the equations for FRET are reviewed along with pertinent core concepts in photophysics. An analogy using simple hydraulics provides a pedagogical tool for the non-aficionado to better understand photochemical kinetics. Ten examples are presented of donor–acceptor systems with donors that exhibit a range of Φf values (0.60, 0.59. 0.21, 0.17, 0.12, 0.118, 0.04, 0.018, 0.007, and 0.003; i.e., 60%–0.3%), yet for each corresponding donor–acceptor pair, the value of Φtrans is at least 0.70 and in some cases nearly 1.00 (i.e., 70%–100%). The systems encompass protein, synthetic inorganic, and synthetic organic architectures. The objectives of this illustrative review are to deepen understanding of FRET and to broaden molecular design considerations by enabling selection from among a far richer set of donors for use in FRET processes.

Lindsey, Jonathan S. (ORCID:0000000248722040)↗
DOE OSTI2021

Accessing Lanthanide-to-Lanthanide Energy Transfer in a Family of Site-Resolved [Ln III Ln III '] Heterodimetallic Complexes

The ligand H 3 L (6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid), which exhibits two different coordination pockets, has been exploited to engender and study energy transfer (ET) in two dinuclear [Ln III Ln III '] analogues of interest, [EuYb] and [NdYb]. Their structural and physical properties have been compared with newly synthesised analogues featuring no possible ET ([EuLu], [NdLu], and [GdYb]) and with the corresponding homometallic [EuEu] and [NdNd] analogues, which have been previously reported. Photophysical data suggest that ET between Eu III and Yb III does not occur to a significant extent, whereas emission from Yb III originates from sensitisation of the ligand. In contrast, energy migration seems to be occurring between the two Nd III centres in [NdNd], as well as in [NdYb], in which Yb III luminescence is thus, in part, sensitised by ET from Nd. This study shows the versatility of this molecular platform to further the investigation of lanthanide-to-lanthanide ET phenomena in defined molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Understanding and controlling the fundamental photochemistry of protonic solar energy conversion (Final Scientific/Technical Report)

The selectivity and activity of most fuel-forming reactions are tunable by the concentration of electrons, holes, protons, and/or hydroxides. That is one reason why traditional solar energy conversion processes are used to drive these reactions, where light directly increases the concentration of electrons and holes. We, instead, took a different approach, using light to increase the concentration of protons and/or hydroxides. For this, we leveraged photophysical and solid-state physics theories, techniques, and design strategies previously developed for the study of traditional solar energy conversion processes. We designed and fabricated several materials platforms based on molecular photoacid and photobase dyes coupled with ion-exchange polymer membranes and assessed their fundamental photoelectrochemistry. We demonstrated control over built-in electric potentials, photovoltages, proton-transfer kinetics, and efficiency limits to our approach. Understanding the basic science of these dye-sensitized protonic membranes and their photochemical mechanisms is of use to the DOE-relevant processes of solar photochemical fuel formation, solar photodialytic desalination, and solar cells. Moreover, functional materials that we developed from this project may be of use to several broad-reaching fields and may provide the foundation for a completely new, inexpensive, and robust solar energy conversion technology.

14 SOLAR ENERGY↗
DOE OSTI2025

Fano Resonance in CO 2 Reduction Catalyst Functionalized Quantum Dots

Molecular catalyst functionalized semiconductor quantum dots (QDs) are a promising modular platform for developing novel hybrid photocatalysts. The interaction between adsorbed catalyst vibrations and the QD electron intraband absorption can influence the photophysical properties of both the QD and the catalysts and potentially their photocatalysis. In CdSe QDs functionalized by the CO 2 reduction catalyst, Re(CO) 3 (4,4’-bipyridine-COOH)Cl, we observe that the transient Fano resonance signal resulting from coupling of the catalyst CO stretching mode and the QD conduction band electron mid-IR intraband absorption appears on an ultrafast time scale and decays with the electron population, irrespective of the occurrence of photoreduced catalysts. The Fano asymmetry factor increases with an increase in the adsorbed catalyst number and a decrease in QD sizes. The latter can be attributed to an enhanced charge transfer interaction between the more strongly quantum-confined QD conduction band and catalyst LUMO levels. These results provide a more in-depth understanding of interactions in excited QD-catalyst hybrid photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Distinct vibrational motions promote disparate excited-state decay pathways in cofacial perylenediimide dimers

A complex interplay of structural, electronic, and vibrational degrees of freedom underpins the fate of molecular excited states. Organic assemblies exhibit a myriad of excited-state decay processes, such as symmetry-breaking charge separation (SB-CS), excimer (EX) formation, singlet fission, and energy transfer. Recent studies of cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) (PDI) multimers demonstrate that slight variations in core substituents and H- or J-type aggregation can determine whether the system follows an SB-CS pathway or an EX one. However, questions regarding the relative importance of structural properties and molecular vibrations in driving the excited-state dynamics remain. Here, we use a combination of two-dimensional electronic spectroscopy, femtosecond stimulated Raman spectroscopy, and quantum chemistry computations to compare the photophysics of two PDI dimers. The dimer with 1,7-bis(pyrrolidin-1′-yl) substituents (5PDI2) undergoes ultrafast SB-CS from a photoexcited mixed state, while the dimer with bis-1,7-(3′,5′-di-t-butylphenoxy) substituents (PPDI2) rapidly forms an EX state. Examination of their quantum beating features reveals that SB-CS in 5PDI2 is driven by the collective vibronic coupling of two or more excited-state vibrations. In contrast, we observe signatures of low-frequency vibrational coherence transfer during EX formation by PPDI2, which aligns with several previous studies. We conclude that key electronic and structural differences between 5PDI2 and PPDI2 determine their markedly different photophysics.

Chemistry↗
DOE OSTI2020

Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers

Recent studies have shown that molecular aggregation structures in precursor solutions of organic photovoltaic (OPV) polymers have substantial influence on polymer film morphology, exciton and charge carrier transport dynamics, and hence, the resultant device performance. To distinguish photophysical impacts due to increasing π-conjugation from chain lengthening and π–π stacking from single/multi chain aggregation in solution and film, we used oligomers of a well-studied charge transfer polymer PTB7 with different lengths as models to reveal intrinsic photophysical properties of a conjugated segment in the absence of inter-segment aggregation. In comparison with previously studied photophysical properties in polymeric PTB7, we found that oligomer dynamics are dominated by a process of planarization of the conjugated backbone into a quinoidal structure that resembles the self-folded polymer and that, when its emission is isolated, this quinoidal excited state resembling the planar polymer chain exhibits substantial charge transfer character via solvent-dependent emission shifts. Furthermore, the oligomers distinctly lack the long-lived charge separated species characteristic of PTB7, suggesting that the progression from charge transfer character in isolated chains to exciton splitting in neat polymer solution is modulated by the interchain interactions enabled by self-folding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Tuning charge carrier dynamics through spacer cation functionalization in layered halide perovskites: an ab initio quantum dynamics study

Dion–Jacobson (DJ) phase two-dimensional (2D) hybrid halide perovskites are promising for environmentally stable optoelectronic device applications due to their attractive photophysical properties, including long charge carrier lifetime and partially suppressed non-radiative losses. However, the atomistic details of the structure–property relationship are severely limited, which substantially restricts the strategic materials designed for these layered halide perovskites (LHPs). Here, we combine nonadiabatic molecular dynamics and time-domain density functional theory to understand the effects of spacer cation functionalization on the ground and excited-state charge carrier dynamics in DJ phase LHPs. Our in-depth study reveals that the fluorination of spacer cations considerably restricts the thermal motions of LHPs at ambient conditions. The compact structure weakens the overall electron–phonon interactions and reduces the thermal fluctuations of the band edges in real-time. These dynamic modifications partially mitigate the non-radiative recombination, prolonging the lifetime of photogenerated charge carriers. The suppressed carrier loss mechanism strongly suggests that the fluorinated spacer cation-based LHPs would exhibit enhanced performance as optoelectronic materials. These systematic simulations of excited state carrier dynamics elaborate that chemically viable functionalization of the spacer cations is a robust approach to improve the photophysical properties of 2D halide perovskites strategically. These insights also guide us to propose a few potential strategies to design highly beneficial spacer cations of LHPs that can be introduced in next-generation optoelectronic devices.

36 MATERIALS SCIENCE↗