Computational Modelling — Conductive Metal-Organic Framework Thin Film Hybrids by Electropolymerization of Monosubstituted Acetylenes

4 measurement groups · 15 results

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

Periodic DFT geometry optimisation, PBE with DFT-D3 in VASP

Density functional theory

DFT/percolation model of BPA@Cu(BDC) SURMOF · Model

Different polymer conformations relaxed under periodic boundary conditions; combined MOF-polymer systems built in N x 1 x 1 MOF supercells; forces converged below 0.01 eV/Angstrom.

Geometry: periodic MOF-polymer supercell
Context: model for polymer conformation inside Cu(BDC) SURMOF channels
Measurement source: SI p.S-11 · Atomistic geometry of the MOF-Polymer system · Figures S10-S11

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Side-group rotation in proposed modified trans-transoid conformation	approximately 30 degrees	—	approximately	Text Approximate	SI p.S-12 · Atomistic geometry · Figure S11

DFT electronic coupling plus Marcus-theory hopping conductance

Density functional theory

DFT/percolation model of BPA@Cu(BDC) SURMOF · Model

Single site represented as 1-hexyne monomer; two monomers in vacuum oriented with triple bonds facing and separated by approximate MOF unit-cell spacing a about 11 Angstrom; B3LYP/def2-SVP in TURBOMOLE.

Temperature: 300
Geometry: monomer dimer model for inter-strand hopping
Context: model for interchain transport between confined oligomers
Measurement source: SI p.S-14 · Quantum chemical computations

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated electron hopping conductance	8.94 x 10-13 S	—	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations
Calculated hole hopping conductance	4.65 x 10-12 S	—	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations
HOMO-HOMO electronic coupling	69.0 ueV	—	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations
LUMO-LUMO electronic coupling	81.7 ueV	—	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations
Electron reorganisation energy	0.57 eV	—	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations
Hole reorganisation energy	0.39 eV	—	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations
Electron inter-strand conductivity	1.79 x 10-3 S m-1	0.00179 S m-1	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations
Hole inter-strand conductivity	9.29 x 10-3 S m-1	0.00929 S m-1	—	Text Exact Reported	SI p.S-14 · Quantum chemical computations

3D bond percolation / interrupted strand conductivity model

Electrical conductivity

DFT/percolation model of BPA@Cu(BDC) SURMOF · Model

Conductivity model where polymers occupy sites in a cubic lattice defined by the MOF; charges move along chains or hop between polymers; assumes sigma_parallel much greater than sigma_perpendicular.

Temperature: 300
Geometry: cubic lattice model of polymer-filled MOF channels
Context: model for macroscopic BPA@SURMOF conductivity
Measurement source: SI p.S-13 · Conductivity Model for MOF-Polymer system · Figures S12-S13

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Experimental macroscopic conductivity used in SI model	0.16 S m-1	0.16 S m-1	—	Text Exact Reported	SI p.S-14 · Figure S13 caption · Figure S13
Bond interruption probability used for upper-bound conductivity	p = 26.6%	0.266 fraction	—	Text Exact Reported	main p.5 · Results and Discussion · Supporting Information
Bond interruption probability corresponding to SI experimental conductivity	23.1%	0.231 fraction	approximately	Text Approximate	SI p.S-15 · Conductivity Model for MOF-Polymer system
Maximum effective conductivity assumed for polyacetylene	38 S m-1	38 S m-1	—	Text Exact Reported	SI p.S-13 · Conductivity Model for MOF-Polymer system · Figure S12
Interchain conductivity used in main-text percolation calculation	sigmaPer = 9.29 x 10-3 S m-1	0.00929 S m-1	—	Text Exact Reported	main p.5 · Results and Discussion · Supporting Information
Upper-bound macroscopic conductivity from percolation model	0.12 S m-1	0.12 S m-1	upper bound	Text Exact Reported	main p.5 · Results and Discussion · Supporting Information

(TD-)DFT Raman calculation, B3LYP/def2-SVP with DFT-D3 in Turbomole; GFN2-xTB pre-relaxation

Raman spectroscopy Density functional theory

DFT/percolation model of BPA@Cu(BDC) SURMOF · Model

MOF represented by a single SBU surrounded by four linkers; monomer placed near a linker; systems relaxed for MOF/monomer and components.

Geometry: molecular cluster model for Raman shifts
Context: free and MOF-confined 1-hexyne calculations
Measurement source: SI p.S-3 · Quantum chemical computations · Figure S9

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source