Chiral Aggregates of Triphenylamine‐Based Dyes for Depleting the Production of Hydrogen Peroxide in the Photochemical Water‐Splitting Process

Adelizzi, Beatrice; Rösch, Andreas T.; Rijen, Daan J. Van; Martire, R. Simone; Esiner, S Serkan; Lutz, Martin; Palmans, Anja R. A.; Meijer, E. W.

doi:10.1002/hlca.201900065

Cited by 5 publications

(3 citation statements)

References 37 publications

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“…In subsequent studies with helically aggregated dye molecules additional features of spin polarization on the characteristics of water splitting became apparent; not only was spin polarization responsible for decreasing the reaction overpotential for the OER, it was shown to inhibit the formation of hydrogen peroxide, as well as other super oxides . These effects have since been shown for other chiral catalysts, − including chiral metal oxides ,,,− and metal sulfides. , As an aside, we note that CISS may account, in part, for the high activity of photosystem II …”

Section: Prevalence Of Ciss and Ciss Implicationsmentioning

confidence: 81%

Chiral Induced Spin Selectivity

Bloom,

Paltiel,

Naaman

et al. 2024

Chem. Rev.

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Since the initial landmark study on the chiral induced spin selectivity (CISS) effect in 1999, considerable experimental and theoretical efforts have been made to understand the physical underpinnings and mechanistic features of this interesting phenomenon. As first formulated, the CISS effect refers to the innate ability of chiral materials to act as spin filters for electron transport; however, more recent experiments demonstrate that displacement currents arising from charge polarization of chiral molecules lead to spin polarization without the need for net charge flow. With its identification of a fundamental connection between chiral symmetry and electron spin in molecules and materials, CISS promises profound and ubiquitous implications for existing technologies and new approaches to answering age old questions, such as the homochiral nature of life. This review begins with a discussion of the different methods for measuring CISS and then provides a comprehensive overview of molecules and materials known to exhibit CISS-based phenomena before proceeding to identify structure−property relations and to delineate the leading theoretical models for the CISS effect. Next, it identifies some implications of CISS in physics, chemistry, and biology. The discussion ends with a critical assessment of the CISS field and some comments on its future outlook.

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Section: Prevalence Of Ciss and Ciss Implicationsmentioning

confidence: 81%

Chiral Induced Spin Selectivity

Bloom,

Paltiel,

Naaman

et al. 2024

Chem. Rev.

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show abstract

“…Considering the emerging work on spintronic applications for example, photoelectrochemical water splitting, where devices functionalised with ac hiral, non-racemic active layer yielded higher currents than for achiral counterparts, [31,33] the presented system provides an promising basis to furtherp robe the impact of supramolecular rather than molecular chirality on materialp roperties. Utilisation in spintronic applicationsw ill be the topicoffuture investigations.…”

Section: Discussionmentioning

confidence: 99%

“…Manifestation of spin‐polarisation in organic materials is described by the so‐called chiral‐induced spin selectivity (CISS) effect [23] . Even though the measured spin polarisation achieved in organic materials is never absolute in the systems described until now, [30] various applications such as water‐splitting, [24, 31–33] enantio‐separation [34, 35] and enantioselective reactions [36] have been realised.…”

Section: Introductionmentioning

confidence: 99%

Helicity Control in the Aggregation of Achiral Squaraine Dyes in Solution and Thin Films

Rösch

Zhu

Robben

et al. 2020

Chemistry A European J

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Squaraine dyes are well knownf or their strong absorption in the visible regime. Reports on chiral squaraine dyes are, however,s carce. To address this gap, we here report two novel chiral squaraine dyes and their achiral counterparts. The presented dyes are aggregated in solution and in thin films. Ad etailed chiroptical study shows that thin films formed by co-assembling the chiral dye with its achiral counterparte xhibit exceptionalp hotophysical properties. The circulard ichroism (CD) of the co-assembled structures reaches am aximum when just 25 %o ft he chiral dye are present in the mixture. The solid structures with the highestr elative CD effect are achieved when the chiral dye is used solely as ad irector,r ather than the structural component. The chiroptical data are further supported by selected spin-filtering measurements using mc-AFM.T hese findings provideapromisingp latform for investigating the relationship between the dissymmetry of as upramolecular structure and emerging material properties rather than ac omparison between ac hiral molecular structure and an achiral counterpart.

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Genesis of the Chirality of Polythiophene Aggregates from Classical Molecular Dynamics

Romagnoli,

Padula

2024

J. Phys. Chem. C

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Conjugated polymers are widely used in electronic devices whose performance is highly dependent on their electronic properties. Properties and performance are influenced by the supramolecular organization of the chromophores constituting the polymer backbone, and identifying structure−property relationships is crucial to design better devices. Polythiophenes (PTs) are among the most-studied polymers, and their ordered aggregation in solution is often induced by the introduction of chiral side chains. This allows using chiroptical spectroscopy, such as electronic circular dichroism, to monitor aggregation, but since experimental atomistic demonstrations of aggregate arrangements are lacking, computational models have been developed to identify the most likely structure. In this work, we simulate the aggregation of chiral polythiophenes by using classical molecular dynamics. Standard simulations show the formation of aggregates with herringbone arrangements, typical of polycyclic aromatic hydrocarbon crystals and also known for P3HT, the most used polythiophene, rather than the chiral H aggregates proposed in the literature. We exploited Hamiltonian Replica Exchange simulations to explore a larger portion of the free energy surface in the search for chiral conformations that would explain the experimentally observed chiroptical response. We identified cisoid and transoid helical structures with intramolecular chirality, without the formation of π−stacked helical aggregates commonly suggested, which resulted unstable. Given past studies of the spectroscopic response of these structures, we assign the genesis of the chirality of polythiophene aggregates to intramolecular arrangements of polymer chains, rather than to interactions among different chains organized in a chiral fashion.

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Chiral Aggregates of Triphenylamine‐Based Dyes for Depleting the Production of Hydrogen Peroxide in the Photochemical Water‐Splitting Process

Cited by 5 publications

References 37 publications

Chiral Induced Spin Selectivity

Chiral Induced Spin Selectivity

Helicity Control in the Aggregation of Achiral Squaraine Dyes in Solution and Thin Films

Genesis of the Chirality of Polythiophene Aggregates from Classical Molecular Dynamics

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