Toward Accurate Calculation of Excitation Energies on Quantum Computers with ΔADAPT-VQE: A Case Study of BODIPY Derivatives DOI

Anton Nykänen,

Leander Thiessen,

Elsi-Mari Borrelli

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(28), P. 7111 - 7117

Published: July 2, 2024

Quantum chemistry simulations offer a cost-effective way to computationally design BODIPY photosensitizers. However, accurate predictions of excitation energies pose challenge for time-dependent density functional theory and equation-of-motion coupled-cluster singles doubles methods. By contrast, reliable can be achieved by multireference quantum methods; unfortunately, their computational cost increases exponentially with the number electrons. Alternatively, computing holds potential an exact simulation photophysical properties in more efficient way. Herein, we introduce state-specific ΔUCCSD-VQE (unitary doubles-variational eigensolver) ΔADAPT-VQE methods which electronically excited state is calculated via non-Aufbau configuration. We show six derivatives that proposed predict are good agreement those from experiments. Due its performance simplicity, believe ΔADAPT will become useful approach photosensitizers on near-term devices.

Language: Английский

Challenges and Future Perspectives in Photocatalysis: Conclusions from an Interdisciplinary Workshop DOI Creative Commons
Sebastian B. Beil, Sylvestre Bonnet, Carla Casadevall

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 2746 - 2766

Published: Aug. 8, 2024

Photocatalysis is a versatile and rapidly developing field with applications spanning artificial photosynthesis, photo-biocatalysis, photoredox catalysis in solution or supramolecular structures, utilization of abundant metals organocatalysts, sustainable synthesis, plastic degradation. In this Perspective, we summarize conclusions from an interdisciplinary workshop young principal investigators held at the Lorentz Center Leiden March 2023. We explore how diverse fields within photocatalysis can benefit one another. delve into intricate interplay between these subdisciplines, by highlighting unique challenges opportunities presented each multidisciplinary approach drive innovation lead to solutions for future. Advanced collaboration knowledge exchange across domains further enhance potential photocatalysis. Artificial photosynthesis has become promising technology solar fuel generation, instance, via water splitting CO

Language: Английский

Citations

19
Efficient Energy and Electron Transfer Photocatalysis with a Coulombic Dyad DOI
Matthias Schmitz, Maria‐Sophie Bertrams, Arne C. Sell

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25799 - 25812

Published: Sept. 3, 2024

Photocatalysis holds great promise for changing the way value-added molecules are currently prepared. However, many photocatalytic reactions suffer from quantum yields well below 10%, hampering transition lab-scale to large-scale or even industrial applications. Molecular dyads can be designed such that beneficial properties of inorganic and organic chromophores combined, resulting in milder reaction conditions improved reactions. We have developed a novel approach obtaining advantages molecular without time- resource-consuming synthesis these tailored photocatalysts. Simply by mixing cationic ruthenium complex with an anionic pyrene derivative water salt bichromophore is produced owing electrostatic interactions. The long-lived triplet state obtained static quantitative energy transfer preorganized complex. exploited this so-called Coulombic dyad catalysis similar reactivity higher photostability compared reference photosensitizers several photooxygenations. In addition, it was shown system also used maximize yield photoredox This due intrinsically cage escape after photoinduced electron purely compounds heavy atom-containing molecules. combination laboratory-scale as mechanistic irradiation experiments detailed spectroscopic investigations provided deep insights into easy-to-use photocatalyst class.

Language: Английский

Citations

11
Iron(III) Carbene Complexes with Tunable Excited State Energies for Photoredox and Upconversion DOI Creative Commons
Joël Wellauer,

Fabienne Ziereisen,

Narayan Sinha

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: April 10, 2024

Substituting precious elements in luminophores and photocatalysts by abundant first-row transition metals remains a significant challenge, iron continues to be particularly attractive owing its high natural abundance low cost. Most complexes known date face severe limitations due undesirably efficient deactivation of luminescent photoredox-active excited states. Two new iron(III) with structurally simple chelate ligands enable straightforward tuning ground state properties, contrasting recent examples, which chemical modification had minor impact. Crude samples feature two luminescence bands strongly reminiscent complex, this observation was attributed dual luminescence, but our case, there is clear-cut evidence that the higher-energy stems from an impurity only red photoluminescence doublet ligand-to-metal charge transfer (2LMCT) genuine. Photoinduced oxidative reductive electron reactions methyl viologen 10-methylphenothiazine occur nearly diffusion-limited kinetics. Photocatalytic not previously reported for compound class, particular C–H arylation diazonium salts aerobic hydroxylation boronic acids, were achieved low-energy light excitation. Doublet–triplet energy (DTET) 2LMCT anthracene annihilator permits proof principle triplet–triplet annihilation upconversion based on molecular photosensitizer. These findings are relevant development featuring photophysical photochemical properties competitive noble-metal-based compounds.

Language: Английский

Citations

10
Highly crystalline benzothiadiazole covalent organic framework for enhanced Cr(VI) photocatalytic reduction by constructing donor-acceptor structure DOI
Chen Wang, Wen Lu, Wenhui Song

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 361, P. 124583 - 124583

Published: Sept. 8, 2024

Language: Английский

Citations

9
Making Mo(0) a Competitive Alternative to Ir(III) in Phosphors and Photocatalysts DOI Creative Commons
Tao Jin, Narayan Sinha,

Dorothee Wagner

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Iridium is used in commercial light-emitting devices and photocatalysis but among the rarest stable chemical elements. Therefore, replacing iridium(III) photoactive molecular complexes with abundant metals of great interest. First-row transition generally tend to yield poorer luminescence behavior, it remains difficult obtain excited states redox properties that exceed those noble-metal-based photocatalysts. Here, we overcome these challenges a nonprecious second-row metal. Tailored coordination spheres for molybdenum(0) lead photoluminescence quantum yields rival photochemical reduction reactions not normally achievable become possible. These developments open new perspectives noble lighting applications Earth-abundant advancing metal-based beyond current limits.

Language: Английский

Citations

2
Rationalizing Photophysics of Co(III) Complexes with Pendant Pyrene Moieties DOI
Jéssica Toigo, Ka-Ming Tong, Rida Farhat

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Pendant organic chromophores have been used to improve the photocatalytic performance of many metal-based photosensitizers, particularly in first-row metals, by increasing π conjugation ligands and lowering energy photoactive absorption band. Using a combination spectroscopic studies computational modeling, we rationalize excited state dynamics Co(III) complex containing pendant pyrene moieties, CoL1, where L1 = 1,1′-(4-(pyren-1-yl)pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium). CoL1 displays higher visible absorptivity, blue luminescence from singlet states compared with CoL0 [L0 1,1′-(pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium)] which moiety is absent. Emissive properties are highly influenced metal center, reducing fluorescence lifetime 5.9 3.5 ns, shift 43 nm. The lower d orbitals Fe(II) drastically affects character state, resulting mixture intraligand charge-transfer (1ILCT) ligand-to-metal (1LMCT) character. Transient experiments revealed that although dark triplet (3ILPyrene) present, it not efficiently populated possesses short nanosecond-scale lifetime. Instead, metal-centered (3MC) dominate decay path 2.4 ps lifetime, no photoactivity toward oxygen formation or triplet–triplet transfer (TTET). This work shows how various factors can influence excited-state dynamics.

Language: Английский

Citations

1
Advances in the Design of Photoactivatable Metallodrugs: Excited State Metallomics DOI Creative Commons
Huayun Shi, Rafael C. Marchi, Peter J. Sadler

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Abstract Photoactivatable metal complexes offer the prospect of novel drugs with low side effects and new mechanisms action to combat resistance current therapy. We highlight recent progress in design platinum, ruthenium, iridium, gold other transition complexes, especially for applications as anticancer anti‐infective agents. In particular, understanding excited state chemistry related identification bioactive species (excited metallomics/pharmacophores) is important. metallodrugs are classified here photocatalysts, photorelease agents ligand‐activated Their activation wavelengths, cellular action, experimental theoretical metallomics states photoproducts discussed explore strategies investigation photoactivatable metallodrugs. These have potential clinical Photodynamic Therapy (PDT), Photoactivated Chemotherapy (PACT) Photothermal (PTT).

Language: Английский

Citations

1
Z-scheme ZnIn2S4-coated La2S3 heterojunction for boosting solar-light induced tetracycline photooxidation and H2 evolution DOI
Hao Peng, Xingqi Luo, Lianyan Wang

et al.

Separation and Purification Technology, Journal Year: 2025, Volume and Issue: unknown, P. 131959 - 131959

Published: Feb. 1, 2025

Language: Английский

Citations

1
Evaluating Singlet Oxygen-Generating Photoresponsive Materials And Their Cross-Reactivity For Photoelectroanalysis DOI
Simone Bassini, Elise Daems, Nick Sleegers

et al.

Sensors and Actuators B Chemical, Journal Year: 2025, Volume and Issue: unknown, P. 137387 - 137387

Published: Feb. 1, 2025

Language: Английский

Citations

1
Molecular engineering and electrolyte optimization strategies for enhanced performance of Ru(ii) polypyridyl-sensitized DSSCs DOI Creative Commons
Islam M. Abdellah

RSC Advances, Journal Year: 2025, Volume and Issue: 15(13), P. 9763 - 9786

Published: Jan. 1, 2025

This review highlights the advantages of optimizing various DSSC components, such as Ru( ii )-polypyridyl photosensitizers, co-adsorbents, electrolytes, electrolyte additives, and counter electrodes, to improve overall performance DSSCs.

Language: Английский

Citations

1