Inhibited interlayer electron transfer in metal ion linked multilayers on mesoporous metal oxide films

Arcidiacono, Ashley; Robb, Alex J.; Masitas, Rafael A.; Salpage, Sahan R.; McLeod, Grace M.; Chen, Jiaqi; Ogunsolu, Omotola O.; Roper, Michael G.; Hanson, Kenneth

doi:10.1016/j.jpap.2021.100088

Cited by 6 publications

(9 citation statements)

References 55 publications

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“…Although ITO|ROD1 is physically located near L D , the data can be modeled with a single and bulk dielectric constant ε st , indicating that the electric double layer does not significantly modulate the electron transfer dynamics. The reorganization energies are similar to those previously reported for acceptors directly linked to ITO or through ionic (O 3 P-CH 2 -PO 3 -Zr(IV)) bridges . This indicates a similar degree of electrolyte reorganization, and the kinetic barrier accompanies interfacial electron transfer for the rigid-rods and for the ionic bridges. …”

Section: Discussionsupporting

confidence: 86%

“…The reorganization energies are similar to those previously reported for acceptors directly linked to ITO or through ionic (O 3 P-CH 2 -PO 3 -Zr(IV)) bridges. 37 This indicates a similar degree of electrolyte reorganization, and the kinetic barrier accompanies interfacial electron transfer for the rigid-rods and for the ionic bridges. i k j j j j j y { z z z z z i k j j j j j j y…”

Section: ■ Discussionmentioning

confidence: 81%

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Reorganization Energies for Interfacial Electron Transfer across Phenylene Ethynylene Rigid-Rod Bridges

Heidari

Loague

Bangle

et al. 2022

ACS Appl. Mater. Interfaces

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A family of three ruthenium bipyridyl rigid-rod compounds of the general form [Ru(bpy) 2 (LL)](PF 6 ) 2 were anchored to mesoporous thin films of tindoped indium oxide (ITO) nanocrystals. Here, LL is a 4-substituted 2,2-bipyridine (bpy) ligand with varying numbers of conjugated phenylenethynylene bridge units between the bipyridine ring and anchoring group consisting of a bis-carboxylated isophthalic group. The visible absorption spectra and the formal potentials, E o (Ru III/II ), of the surface anchored rigid-rods were insensitive to the presence of the phenylene ethynylene bridge units in 0.1 M tetrabutyl ammonium perchlorate acetonitrile solutions (TBAClO 4 /CH 3 CN). The conductive nature of the ITO enabled potentiostatic control of the Fermi level and hence a means to tune the Gibbs free energy change, −ΔG°, for electron transfer from the ITO to the rigid-rods. Pseudo-rate constants for this electron transfer reaction increased as the number of bridge units decreased at a fixed −ΔG°. With the assumption that the reorganization energy, λ, and the electronic coupling matrix element, H ab , were independent of the applied potential, rate constants measured as a function of −ΔG°and analyzed through Marcus− Gerischer theory provided estimates of H ab and λ. In rough accordance with the dielectric continuum theory, λ was found to increase from 0.61 to 0.80 eV as the number of bridge units was increased. In contrast, H ab decreased markedly with distance from 0.54 to 0.11 cm −1 , consistent with non-adiabatic electron transfer. Comparative analysis with previously published studies of bridges with an sp 3 -hybridized carbon indicated that the phenylene ethynylene bridge does not enhance electronic coupling between the oxide and the rigid-rod acceptor. The implications of these findings for practical applications in solar energy conversion are specifically discussed.

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Section: Discussionsupporting

confidence: 86%

Section: ■ Discussionmentioning

confidence: 81%

Reorganization Energies for Interfacial Electron Transfer across Phenylene Ethynylene Rigid-Rod Bridges

Heidari

Loague

Bangle

et al. 2022

ACS Appl. Mater. Interfaces

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“…While interlayer electron transfer has been observed, 50 the increased distance and geometric constraint imparted by the metal ion linkage can also hinder electron transfer. 48 Consequently, the post injection cation resides on A and is likely the site of regeneration where access by the mediator is still possible due to the lower surface coverage of Os relative to A (∼7 : 1). 15…”

Section: Resultsmentioning

confidence: 99%

“…This k ET is orders of magnitude larger than previously observed for diphenyl anthracene-Zn-Pt(II) porphyrin multilayer. 34,47 Presumably any decreases in rate due to increased spatial separation between the anthracene and osmium transition dipole moments 48 are offset by the near unity spectral overlap between emission from A and absorption of Os. This observation further emphasizes the utility of an absorption gap between the Soret and Q bands of metalloporphyrins and their continued popularity as sensitizers for TTA-UC.…”

Section: Energy and Electron Transfer Dynamicsmentioning

confidence: 99%

Harnessing near-infrared lightviaS₀to T₁sensitizer excitation in a molecular photon upconversion solar cell

et al. 2022

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“…An important aspect for the rational design of these assemblies is knowledge of molecular structure–function relationships, i.e., controlling the structure of each layer is a prerequisite to obtaining their desired function(s). For example, the rate and efficiency of interlayer energy transfer are directly dependent on the distance and orientation between the donor and acceptor chromophores, as dictated by the position of the metal ion binding motif. , Likewise, electron transfer between molecular layers and an electrode substrate can be enhanced or inhibited using strategic selection of the metal ion, molecular components, and substrate porosity. − …”

Section: Introductionmentioning

confidence: 99%

Molecular Orientation and Energy Transfer Dynamics of a Metal Oxide Bound Self-Assembled Trilayer

et al. 2023

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Self-assembly of molecular multilayers via metal ion linkages has become an important strategy for interfacial engineering of metalloid and metal oxide (MO x ) substrates, with applications in numerous areas, including energy harvesting, catalysis, and chemical sensing. An important aspect for the rational design of these multilayers is knowledge of the molecular structure–function relationships. For example, in a multilayer composed of different chromophores in each layer, the molecular orientation of each layer, both relative to the adjacent layers and the substrate, influences the efficiency of vectorial energy and electron transfer. Here, we describe an approach using UV–vis attenuated total reflection (ATR) spectroscopy to determine the mean dipole tilt angle of chromophores in each layer in a metal ion-linked trilayer self-assembled on indium-tin oxide. To our knowledge, this is the first report demonstrating the measurement of the orientation of three different chromophores in a single assembly. The ATR approach allows the adsorption of each layer to be monitored in real-time, and any changes in the orientation of an underlying layer arising from the adsorption of an overlying layer can be detected. We also performed transient absorption spectroscopy to monitor interlayer energy transfer dynamics in order to relate structure to function. We found that near unity efficiency, sub-nanosecond energy transfer between the third and second layer was primarily dictated by the distance between the chromophores. Thus, in this case, the orientation had minimal impact at such proximity.

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Inhibited interlayer electron transfer in metal ion linked multilayers on mesoporous metal oxide films

Cited by 6 publications

References 55 publications

Reorganization Energies for Interfacial Electron Transfer across Phenylene Ethynylene Rigid-Rod Bridges

Reorganization Energies for Interfacial Electron Transfer across Phenylene Ethynylene Rigid-Rod Bridges

Harnessing near-infrared lightviaS₀to T₁sensitizer excitation in a molecular photon upconversion solar cell

Molecular Orientation and Energy Transfer Dynamics of a Metal Oxide Bound Self-Assembled Trilayer

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Inhibited interlayer electron transfer in metal ion linked multilayers on mesoporous metal oxide films

Cited by 6 publications

References 55 publications

Reorganization Energies for Interfacial Electron Transfer across Phenylene Ethynylene Rigid-Rod Bridges

Reorganization Energies for Interfacial Electron Transfer across Phenylene Ethynylene Rigid-Rod Bridges

Harnessing near-infrared lightviaS0to T1sensitizer excitation in a molecular photon upconversion solar cell

Molecular Orientation and Energy Transfer Dynamics of a Metal Oxide Bound Self-Assembled Trilayer

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Harnessing near-infrared lightviaS₀to T₁sensitizer excitation in a molecular photon upconversion solar cell