Computational Modelling — Reaction-Type-Dependent Behavior of Redox-Hopping in MOFs─Does Charge Transport Have a Preferred Direction?

4 measurement groups · 18 results

Reported values remain attached to the sample, method, conditions, extraction quality and source location that produced them.

DFT reorganisation-energy calculations

Density functional theory

[Ru(bpy)2(bpy-COOH)] charge-state DFT models · Model

UB3LYP-D3BJ/6-311G(d,p)[H,C,N,O]/SDD[Ru] in Gaussian16, with and without MeCN PCM; standard four-point method on adiabatic potential-energy surfaces.

Atmosphere: gas/no PCM and MeCN PCM models
Geometry: molecular redox-centre model
Context: Model for anchored Ru redox centre in target MOF.
Measurement source: p006-p007 · Density Functional Theory · Table S2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Intramolecular reorganisation energy, oxidation, MeCN PCMMarked as a best value within this paper	0.1159 eV	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S2
Intramolecular reorganisation energy, reduction, MeCN PCMMarked as a best value within this paper	0.2983 eV	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S2
Intramolecular reorganisation energy, oxidation, no PCM	0.0925 eV	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S2
Intramolecular reorganisation energy, reduction, no PCM	0.1858 eV	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S2
Literature self-exchange rate context, Ru(bpy)3 oxidation	1.0 x 10^8 M^-1 s^-1	—	—	Text Rounded Reported	p005 / article page 11923 · Results and discussion
Literature self-exchange rate context, Ru(bpy)3 reduction	4.2 x 10^8 M^-1 s^-1	—	—	Text Rounded Reported	p005 / article page 11923 · Results and discussion

DFT optimized-structure RMSD comparison

Density functional theory

[Ru(bpy)2(bpy-COOH)] charge-state DFT models · Model

RMSD of optimized 1+ and 3+ structures relative to optimized 2+ [RuII(bpy)2(bpy-COOH)]2+, with and without MeCN PCM.

Atmosphere: gas/no PCM and MeCN PCM models
Geometry: molecular redox-centre model
Context: Model for redox-state structural reorganisation.
Measurement source: p007 · Density Functional Theory · Table S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
RMSD 2+ to 3+, MeCN PCM	0.1442 A	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S1
RMSD 2+ to 1+, MeCN PCM	0.1037 A	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S1
RMSD 2+ to 3+, no PCM	0.1053 A	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S1
RMSD 2+ to 1+, no PCM	0.1689 A	—	—	SI Table Exact Reported	p007 · Density Functional Theory · Table S1

Structural/geometric hopping-distance model

Ru-NU-1000 hopping-distance structural model · Model

Uniform redox-centre distribution in NU-1000 hexagonal tunnels used to estimate hole and electron hopping distances.

Atmosphere: model calculation
Geometry: NU-1000 hexagonal tunnel model
Context: Ru-NU-1000 structural model.
Measurement source: p006 / article page 11924 · Results and discussion · Figure 6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Delocalised bpy electron-cloud hopping distanceMarked as a best value within this paper	~10.0 A	—	—	Text Approximate	p006 / article page 11924 · Results and discussion · Figure 6
Direct bpy-COOH-to-bpy-COOH hopping distance	~20.5 A	—	—	Text Approximate	p006 / article page 11924 · Results and discussion · Figure 6
Hole-transport Ru-to-Ru hopping distance	approximately 17.3 A	—	—	Text Approximate	p005 / article page 11923 · Results and discussion · Figure 6

Scholz-model parameter calculation

Ru-NU-1000 hopping-distance structural model · Model

SI calculates NU-1000 molar volume, electron hopping distance, ion diffusion distance, particle interface parameter, and particle count used in model fitting.

Atmosphere: model calculation
Geometry: hexagonal Ru-NU-1000 particle model
Context: Transport-model inputs for target MOF.
Measurement source: p006 · Quantification of De and Di in Ru-NU-1000 · Figure S8

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Scholz ion diffusion distance Delta x0	17.389 A	—	—	Text Exact Reported	p006 · Quantification of De and Di
Scholz electron hopping distance Delta z0	20.839 A	—	—	Text Exact Reported	p006 · Quantification of De and Di
NU-1000 density used in model	0.473 g/cm3	—	—	Text Exact Reported	p006 · Quantification of De and Di
NU-1000 molar mass used in model	2180 g/mol	—	—	Text Exact Reported	p006 · Quantification of De and Di
NU-1000 molar volume used in model	4609.598 cm3/mol	—	—	Text Exact Reported	p006 · Quantification of De and Di