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Alkyl Pyridinium Iodocuprate(I) Clusters: Structural Types and Charge Transfer Behavior.

ABSTRACT: The reaction of copper(I) iodide (CuI) and N-alkyl pyridinium (RPy⁺, R = H, Me, Et, n-propyl = Pr, n-butyl = Bu, n-pentyl = Pn, and n-hexyl = Hx) or N-butyl-3-substituted pyridinium (N-Bu-3-PyX⁺, X = I, Br, Cl, CN, and OMe) iodide salts yielded pyridinium iodocuprate(I) salts. Crystal structures of iodocuprate ions coupled with RPy⁺ include {Cu₃I₆ ^3-} _n (R = H), {Cu₂I₃ ^-} _n (R = Me), {Cu₃I₄ ^-} _n (R = Et), {Cu₆I₈ ^2-} _n (R = Pr), and {Cu₅I₇ ^2-} _n (R = Bu, Pn, Hx). The [N-Bu-3-PyX]⁺ ions were typically paired with the 1-D chain {Cu₅I₇ ^2-} _n . Diffuse reflectance spectroscopy performed on the [N-Bu-3-PyX]⁺ iodocuprate salts revealed that increasing the electron withdrawing capacity of the [N-Bu-3-PyX]⁺ system reduced the absorption edge of the iodocuprate salt. Variable temperature emission spectra of several [N-Bu-3-PyX]⁺ compounds revealed two emission peaks, one consistent with a cluster-centered halide to metal charge transfer and the other consistent with an intermolecular mixed halide/metal charge transfer to the organic cation. The emission intensity and emission wavelength of the mixed halide/metal to cation charge transfer depends on the organic cation substitution.

SUBMITTER: Wheaton AM

PROVIDER: S-EPMC6644175 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Alkyl Pyridinium Iodocuprate(I) Clusters: Structural Types and Charge Transfer Behavior.

Wheaton Amelia M AM Streep Michaela E ME Ohlhaver Christopher M CM Nicholas Aaron D AD Barnes Francis H FH Patterson Howard H HH Pike Robert D RD

ACS omega 20181112 11

The reaction of copper(I) iodide (CuI) and N-alkyl pyridinium (RPy+, R = H, Me, Et, n-propyl = Pr, n-butyl = Bu, n-pentyl = Pn, and n-hexyl = Hx) or N-butyl-3-substituted pyridinium (N-Bu-3-PyX+, X = I, Br, Cl, CN, and OMe) iodide salts yielded pyridinium iodocuprate(I) salts. Crystal structures of iodocuprate ions coupled with RPy+ include {Cu3I6 3-} n (R = H), {Cu2I3< ...[more]

PMID: 31458189

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Project description:Semiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.

Dataset Information

Alkyl Pyridinium Iodocuprate(I) Clusters: Structural Types and Charge Transfer Behavior.

Publications

Alkyl Pyridinium Iodocuprate(I) Clusters: Structural Types and Charge Transfer Behavior.

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