Bridge improvement work: maximising non-linear optical performance in polyoxometalate derivatives

Jones, Claire F.; Hood, Bethany R.; de Coene, Yovan; Lopez-Poves, Ivan; Champagne, Benoît; Clays, Koen; Fielden, John

doi:10.1039/d3cc05433k

Cited by 4 publications

(1 citation statement)

References 37 publications

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“…Polyoxometalates (POMs) are a class of nanostructured transition metal oxide molecular clusters with a clear composition, diverse structures, adjustable structure volume, flexible scaffolds, easy derivatization, adjustable valence state, and reversible redox properties. Therefore, they are attractively researched in electrochemical energy storage, , catalytic, , medicine, , photo/electro-chromics, − and nature . Different from the traditional transition metal oxides, POMs are able to store multiple electrons during the charging/discharging process, known as an “electron sponge”.…”

Section: Introductionmentioning

confidence: 99%

Huge Electron Sponge of Polyoxometalate toward Advanced Lithium-Ion Storage

Tang,

Liu,

et al. 2024

Langmuir

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Section: Introductionmentioning

confidence: 99%

Huge Electron Sponge of Polyoxometalate toward Advanced Lithium-Ion Storage

Tang,

Liu,

et al. 2024

Langmuir

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Unraveling the structure–property relationship of novel thiophene and furan‐fused cyclopentadienyl chromophores for nonlinear optical applications

Sun

2024

J Comput Chem

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Development of organic nonlinear optical materials has become progressively more important due to their emerging applications in new‐generation photonic devices. A novel series of chromophores based on innovative thiophene and furan‐fused cyclopentadienyl bridge with various powerful donor and acceptor moieties were designed and theoretically investigated for applications in nonlinear optics. To unravel the structure–property relationship between this new push‐pull conjugated systems and their nonlinear optical property, multiple methods, including density of states analysis, coupled perturbed Kohn–Sham (CPKS) method, sum‐over‐states (SOS) model, the two‐level model (TSM), hyperpolarizability density analysis, and the (hyper)polarizability contribution decomposition, were performed to comprehensively investigated the nonlinear optical and electronic properties of this new π‐system. Due to excellent charge transfer ability of new bridge and distinctive structure of donor and acceptor, the designed chromophores exhibit deep HOMO levels, low excitation energy, high dipole moment difference and large hyperpolarizability, indicating the appealing air‐stable property and remarkable electrooptic performance of them. Importantly, THQ‐CS‐A3 and PA‐CS‐A3 shows outstanding NLO response properties with βtot value of 6953.9 × 10−30 and 5066.0 × 10−30 esu in AN, respectively. The influence of the push‐pull strength, the heterocycle and the π‐conjugation of new bridge on the nonlinear optical properties of this novel powerful systems are clarified. This new series of chromophores exhibit remarkable electro‐optical Pockels and optical rectification effect. More interestingly, PA‐CS‐A3 and THQ‐CS‐A2 also show appealing SHG effect. This study will help people understand the nature of nonlinear optical properties of innovative heteroarene‐fused based cyclopentadienyl chromophores and offer guidance for the rational design of chromophores with outstanding electrooptic (EO) performance in the future.

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Synthesis and Optical and Nonlinear Optical Properties of Linear and Two-Dimensional Charge Transfer Chromophores Based on Polyoxometalates

Hood,

de Coene,

Jones

et al. 2024

Inorg. Chem.

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We present the first study of arylimido-polyoxometalate nonlinear optical (NLO) chromophores with two-dimensional (2D) structures, and a comparison with one-dimensional analogues, through the synthesis of a family of arylimido-hexamolybdate derivatives where one or two polyoxometalate (POM) acceptors are connected to a tolyl-amino donor through phenyl bridges. Electronic absorption spectra and TD-DFT calculations reveal significant red-shifts in ligand-to-polyoxometalate charge transfer (LPCT) absorption bands for the 2D species compared to linear, dipolar analogues, consistent with the involvement of a larger conjugated (bridge + POM) system in the transitions. Electrochemical measurements indicate reversible, one-electron processes for the POM acceptors with class II mixed valence behavior observed where the POMs are connected to the same aryl ring and electronic isolation of the acceptors when they are on separate rings. Molecular first hyperpolarizabilities β have been determined using hyper-Rayleigh scattering at 1064 and 1200 nm: for the most active compound, the HRS measurements and depolarization studies reveal a strongly 2D, off-diagonal response (β 0,zzz = 190 × 10 −30 esu; β 0,zyy = −56.5 × 10 −30 esu), consistent with the wide A−D−A angle and TD-DFT computed electronic transitions, which show both phenyl bridges and POMs equally involved in the acceptor orbitals.

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Bridge improvement work: maximising non-linear optical performance in polyoxometalate derivatives

Abstract: New phenyl and stilbene-bridged polyoxometalate (POM) charge-transfer chromophores with diphenylamino donor groups produce, respectively, the highest intrinsic and absolute quadratic hyperpolarisabilities measured for such species. The β0,zzz obtained for phenyl...

Cited by 4 publications

References 37 publications

Huge Electron Sponge of Polyoxometalate toward Advanced Lithium-Ion Storage

Huge Electron Sponge of Polyoxometalate toward Advanced Lithium-Ion Storage

Unraveling the structure–property relationship of novel thiophene and furan‐fused cyclopentadienyl chromophores for nonlinear optical applications

Synthesis and Optical and Nonlinear Optical Properties of Linear and Two-Dimensional Charge Transfer Chromophores Based on Polyoxometalates

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