Direct detection of spin polarization in photoinduced charge transfer through a chiral bridge

Privitera, Alberto; Macaluso, Emilio; Chiesa, Alessandro; Gabbani, Alessio; Faccio, Davide; Giuri, Demetra; Briganti, Matteo; Giaconi, Niccolò; Santanni, Fabio; Jarmouni, Nabila; Poggini, Lorenzo; Mannini, Matteo; Chiesa, Mario; Tomasini, Claudia; Pineider, Francesco; Salvadori, Enrico; Carretta, S.; Sessoli, Roberta

doi:10.1039/d2sc03712b

Cited by 27 publications

(52 citation statements)

References 80 publications

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“…Only recently, a few research groups have focused their attention on the direct detection of the CISS effect at the molecular level. 8,11,16,17 In principle, this could be achieved by probing the spin polarisation arising from photoinduced electron transfer (ET) in D-χ-A architectures, where D is an electron donor, A is an electron acceptor, and χ is a chiral bridge. 8,11,16 For these studies, time-resolved Electron Paramagnetic Resonance (trEPR) is the technique of choice, as it allows to probe any CISS-dependent signature on the behaviour of the photogenerated radical pairs, including their coherent spin dynamics.…”

Section: Introductionmentioning

confidence: 99%

“…8,11,16,17 In principle, this could be achieved by probing the spin polarisation arising from photoinduced electron transfer (ET) in D-χ-A architectures, where D is an electron donor, A is an electron acceptor, and χ is a chiral bridge. 8,11,16 For these studies, time-resolved Electron Paramagnetic Resonance (trEPR) is the technique of choice, as it allows to probe any CISS-dependent signature on the behaviour of the photogenerated radical pairs, including their coherent spin dynamics. 8,17,18 Interestingly, trEPR measurements also have great potential for studying CISS in randomly oriented samples.…”

Section: Introductionmentioning

confidence: 99%

“…8,17,18 Interestingly, trEPR measurements also have great potential for studying CISS in randomly oriented samples. 16 If successful, the direct detection of the CISS effect via EPR spectroscopy will promote the development of a more robust theoretical description of the phenomenon, with no need to model interfaces, and the formulation of clear and handy guidelines for the synthesis of CISS-active materials. Behind the excitement of these promises, however, lays the stark reality.…”

Section: Introductionmentioning

confidence: 99%

“…In fact, the quasi-totality of the available results comes from theoretical works, 8,18,19 and the very few experimental attempts present in literature are not conclusive yet. 16 The main challenge originates from the complexity of developing model systems exhibiting at the same time good ET efficiency, effective chiral spin filtering, and charge transfer (CT) states lasting hundreds of ns, as required for trEPR investigation. 16 Our previous work identified a hybrid organic-inorganic system comprising a CdSe quantum dot (QD) and C60 fullerene as D and A, respectively, covalently linked through a saturated oligopeptide helical bridge (χ).…”

Section: Introductionmentioning

confidence: 99%

“…16 The main challenge originates from the complexity of developing model systems exhibiting at the same time good ET efficiency, effective chiral spin filtering, and charge transfer (CT) states lasting hundreds of ns, as required for trEPR investigation. 16 Our previous work identified a hybrid organic-inorganic system comprising a CdSe quantum dot (QD) and C60 fullerene as D and A, respectively, covalently linked through a saturated oligopeptide helical bridge (χ). 16 Although this architecture looks promising, the photoexcited state of the inorganic QD has complex spin properties.…”

Section: Introductionmentioning

confidence: 99%

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Challenges in the direct detection of chirality-induced spin selectivity: investigation of foldamer-based donor/acceptor dyads

Privitera

Faccio

Giuri

et al. 2022

Preprint

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Over the past two decades, the chirality-induced spin selectivity (CISS) effect was reported in several experiments disclosing a unique connection between chirality and electron spin. Recent theoretical works have highlighted time-resolved Electron Paramagnetic Resonance (trEPR) as a powerful tool to directly detect the spin polarisation resulting from CISS. Because of the absence of interfaces with conducting electrodes, such spectroscopic evidence could provide a clear understanding of how CISS works at the intramolecular level. Experimental results have demonstrated the potential of this approach for detecting a spin-polarised photoinduced electron transfer (ET) in hybrid systems comprising a CdSe quantum dot as an electron donor (D) connected by a chiral linker (χ) to a fullerene derivative as an electron acceptor (A). However, the study of the ET process in fully organic D-χ-A dyads holds tremendous potential for the unambiguous detection of CISS. Here, we report a first attempt performed using novel D-χ-A dyads, comprising pyrene (D) and fullerene (A) connected by chiral saturated peptide bridges (χ) of different length and electric dipole moment. The dyads are investigated by an array of techniques, including cyclic voltammetry, optical spectroscopies, and trEPR. Despite the promising energy alignment of the electronic levels and the evidence of luminescence quenching, trEPR does not detect a significant ET highlighting the challenges of spectroscopic detection of CISS. However, the analysis allows the formulation of guidelines for the design of chiral organic model systems suitable to directly probe CISS-polarised ET.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Challenges in the direct detection of chirality-induced spin selectivity: investigation of foldamer-based donor/acceptor dyads

Privitera

Faccio

Giuri

et al. 2022

Preprint

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Chirality‐Induced Spin Selectivity: An Enabling Technology for Quantum Applications

et al. 2023

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Molecular spins are promising building blocks of future quantum technologies thanks to the unparalleled flexibility provided by chemistry, which allows the design of complex structures targeted for specific applications. However, their weak interaction with external stimuli makes it difficult to access their state at the single‐molecule level, a fundamental tool for their use, for example, in quantum computing and sensing. Here, an innovative solution exploiting the interplay between chirality and magnetism using the chirality‐induced spin selectivity effect on electron transfer processes is foreseen. It is envisioned to use a spin‐to‐charge conversion mechanism that can be realized by connecting a molecular spin qubit to a dyad where an electron donor and an electron acceptor are linked by a chiral bridge. By numerical simulations based on realistic parameters, it is shown that the chirality‐induced spin selectivity effect could enable initialization, manipulation, and single‐spin readout of molecular qubits and qudits even at relatively high temperatures.

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Metalloporphyrins as Building Blocks for Quantum Information Science

Santanni,

Privitera

2024

Advanced Optical Materials

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The intrinsic quantum nature of molecules opens exciting opportunities for developing the field of quantum information science. In this context, porphyrins stand out as ideal building blocks for quantum technologies thanks to their unique optical and electrical properties as well as their capacity to accommodate metal atoms and ions. This review bridges the chemistry and physics of porphyrins, providing an overview of recent advances in porphyrin‐based molecular qubits. Starting from qubits, the review explores the potential of porphyrin units to combine, leading to the formation of quantum logic gates and hierarchical higher‐dimensional structures. Next, the exploitation of porphyrins' unique photophysical properties for realizing long‐lived high spin states is examined. These states are promising for the photogeneration of multi‐level systems and the optical initialization and control of molecular qubits. With a critical eye on the current state‐of‐the‐art, the review elucidates the future perspectives of porphyrins for advancing quantum technologies.

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Direct detection of spin polarization in photoinduced charge transfer through a chiral bridge

Abstract: It is well assessed that the charge transport through a chiral potential barrier can result in spin-polarized charges. The possibility of driving this process through visible photons holds tremendous potential...

Cited by 27 publications

References 80 publications

Challenges in the direct detection of chirality-induced spin selectivity: investigation of foldamer-based donor/acceptor dyads

Challenges in the direct detection of chirality-induced spin selectivity: investigation of foldamer-based donor/acceptor dyads

Chirality‐Induced Spin Selectivity: An Enabling Technology for Quantum Applications

Metalloporphyrins as Building Blocks for Quantum Information Science

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