Computational Modelling — Rational modifications of PCN-700 to induce electrical conductivity: A computational study

11 measurement groups · 34 results

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

DFT geometry optimisation, PDOS and orbital-density analysis for Ce-substituted M-PCN-700-DHBQ.

Density functional theory

DFT Ce-PCN-700-DHBQ model · Model

Ce4+ substituted for Zr4+ in PCN-700-DHBQ to lower metal energy levels and inspect Ce/DHBQ/cluster-oxygen orbital contributions.

Atmosphere: not_applicable
Geometry: periodic MOF model
Context: model_system
Measurement source: main p.7, article p.108 · Metal substitution · Fig. 5c; Fig. 6; Fig. S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated bandgap of Ce-PCN-700-DHBQ	2.11 eV	—	—	Text Exact Reported	main p.7, article p.108 · Metal substitution · Fig. 5c
Ce 4f and DHBQ LUCO overlap	Ce 4f band directly overlaps with original LUCO contributed by DHBQ linkers	—	—	Text Qualitative	main p.7, article p.108 · Metal substitution · Fig. 5c; Fig. 6
Cluster oxygen contribution in Ce-PCN-700-DHBQ	cluster oxygen contribution is insignificant and insufficient for CT	—	—	Text Qualitative	main p.8, article p.109 · Metal substitution · Fig. S4

Gaussian09 cluster DFT geometry optimisation and binding-energy calculation; B3LYP functional; 6-31G basis for C/H/O and LANL2DZ for Zr.

Density functional theory

Finite Zr6O4(OH)4-DHBQ cluster coordination model · Model

Finite Zr6O4(OH)4 cluster with formate modulators; DHBQ linker, metal cluster, and complexes optimised separately; B.E. = Ecomplex - (Emetal cluster + Elinker).

Atmosphere: not_applicable
Geometry: finite cluster model
Context: model_system
Measurement source: main p.3, article p.104 · DHBQ coordination mode analysis

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
1:1 DHBQ coordination stability advantage over 1:2 coordination	1:1 coordination was more stable than 1:2 coordination by 27.7 kJ mol-1	—	—	Text Exact Reported	main p.4, article p.105 · Sequential linker installation of DHBQ in PCN-700 · Fig. 3

Gaussian09 cluster DFT on one DHBQ linker positioned between two Zr6O4(OH)4 clusters.

Density functional theory

Finite Zr6O4(OH)4-DHBQ cluster coordination model · Model

One linker vacant site left exposed on each cluster; other three sites capped with formate modulators; seven DHBQ coordination configurations compared.

Atmosphere: not_applicable
Geometry: two-cluster finite model
Context: model_system
Measurement source: main p.5, article p.106 · Sequential linker installation of DHBQ in PCN-700 · Table S1; Fig. S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Energy barrier between optimised bent and aligned DHBQ configuration	3.13 kJ mol-1	—	—	Text Exact Reported	main p.5, article p.106 · Sequential linker installation of DHBQ in PCN-700 · Fig. S2
BDC comparison binding energy in two-cluster model	approximately -655 kJ/mol from Fig. S1	—	visual estimate from rendered SI bar chart	Figure Axis Approximate	SI p.4 · Figure S1 · Fig. S1
DHBQ two-cluster configuration 1 binding energyMarked as a best value within this paper	approximately -700 kJ/mol from Fig. S1	—	visual estimate from rendered SI bar chart	Figure Axis Approximate	SI p.4 · Figure S1 · Fig. S1
DHBQ 1:1 two-cluster binding energy at 25 degree transverse angular offsetMarked as a best value within this paper	approximately -690 kJ/mol from Fig. S2	—	visual estimate from rendered SI bar chart	Figure Axis Approximate	SI p.5 · Figure S2 · Fig. S2
DHBQ 1:1 two-cluster binding energy at 0 degree transverse angular offset	approximately -684 kJ/mol from Fig. S2	—	visual estimate from rendered SI bar chart	Figure Axis Approximate	SI p.5 · Figure S2 · Fig. S2

DFT geometry optimisation, PDOS and orbital-density analysis for linker-saturated Ce-PCN-700-DHBQ.

Density functional theory

DFT linker saturated Ce-PCN-700-DHBQ model · Model

DHBQ placed at z-axial and remaining x/y-axial linker vacant sites; PDOS separates z-DHBQ and x/y-DHBQ contributions; orbital-density plots analysed for LUCO, LUCO+1 and LUCO+2.

Atmosphere: not_applicable
Geometry: periodic MOF model
Context: model_system
Measurement source: main p.8, article p.109 · Linker saturation · Fig. 7; Fig. 8

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated bandgap of linker saturated Ce-PCN-700-DHBQMarked as a best value within this paper	2.09 eV	—	—	Text Exact Reported	main p.8, article p.109 · Linker saturation · Fig. 7
Continuous z-axial CT pathway in linker saturated Ce-PCN-700-DHBQMarked as a best value within this paper	LUCO, LUCO+1 and LUCO+2 effectively secure a continuous charge transport pathway in the z-axial direction	—	—	Caption Qualitative	main p.9, article p.110 · Linker saturation · Fig. 8
LUCO+1 energy offset from LUCO	about 0.14 eV apart in energy from LUCO	—	—	Text Approximate	main p.8, article p.109 · Linker saturation · Fig. 7; Fig. 8
LUCO+2 energy offset from LUCO	about 0.18 eV apart in energy from LUCO	—	—	Text Approximate	main p.8, article p.109 · Linker saturation · Fig. 7; Fig. 8

Flexible molecular dynamics using LAMMPS, UFF, Lennard-Jones and Coulomb potentials, QEq framework charges, and Gaussian09-derived linker charges.

Molecular dynamics

Flexible MD PCN-700 linker-installation series · Model

0.1 ns NVT initialisation, 1 ns NPT equilibration, 0.1 ns NPT annealing, 0.1 ns NPT production at 1 atm; high reaction temperature 1000 K for all linkers except BPDC at 1500 K; annealed to 298 K.

Temperature: 1000 K reaction-temperature stage; BPDC 1500 K; annealed to 298 K
Atmosphere: not_applicable
Geometry: periodic all-atomic PCN-700 model
Context: model_system
Measurement source: main p.3, article p.104 · Molecular dynamics · Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Flexible MD BDC-installed PCN-700 c parameter	14.99 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD BPDC-installed PCN-700 c parameter	19.30 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD DHBQ-installed PCN-700 a parameter	24.48 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD DHBQ-installed PCN-700 b parameter	24.47 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD DHBQ-installed PCN-700 c parameter	12.97 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD DHBQ-installed PCN-700 unit-cell volume	7773 A3	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD FA-installed PCN-700 a parameter	24.66 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD FA-installed PCN-700 b parameter	24.34 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD FA-installed PCN-700 c parameter	12.92 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD FA-installed PCN-700 unit-cell volume	7756 A3	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1
Flexible MD NDC-installed PCN-700 c parameter	17.15 A	—	—	Table Exact Reported	main p.5, article p.106 · Table 1 · Table 1

Periodic all-atomic DFT geometry optimisation and DOS with VASP, PAW, PBEsol and HSE06.

Density functional theory

DFT PCN-700-BDC reference model · Model

Reference PCN-700-BDC model optimised and analysed for comparison to DHBQ installation.

Atmosphere: not_applicable
Geometry: periodic MOF model
Context: model_system
Measurement source: main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Fig. S3

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated bandgap of PCN-700-BDC	4.11 eV	—	—	Text Exact Reported	main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Fig. 4

Periodic all-atomic DFT geometry optimisation, DOS and PDOS with VASP/PBEsol/HSE06.

Density functional theory

DFT PCN-700-DHBQ model with z-axial DHBQ · Model

DHBQ fully coordinated at z-axial vacant sites; x/y vacant sites modulated with water and hydroxyl groups; DOS and PDOS used to locate frontier orbitals.

Atmosphere: not_applicable
Geometry: periodic MOF model
Context: model_system
Measurement source: main p.6, article p.107 · Electronic properties of PCN-700-DHBQ · Fig. 4; Fig. 5a; Fig. 6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated bandgap of PCN-700-DHBQ	2.49 eV	—	—	Text Exact Reported	main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Fig. 4
Frontier orbital composition in PCN-700-DHBQ	HOCO and LUCO exclusively traced back to DHBQ linkers; Zr ions and cluster oxygen atoms do not comprise these orbitals	—	—	Text Qualitative	main p.6, article p.107 · Electronic properties of PCN-700-DHBQ · Fig. 5a; Fig. 6

Periodic all-atomic DFT geometry optimisation and DOS with VASP, PAW, PBEsol, single Gamma-point sampling; HSE06 hybrid functional for bandgap prediction.

Density functional theory

DFT PCN-700 reference model · Model

SCF convergence 1e-7 eV, ionic force convergence 0.01 eV A-1, Gaussian smearing sigma 0.05 eV, vacuum-aligned DOS.

Atmosphere: not_applicable
Geometry: periodic MOF model
Context: model_system
Measurement source: main p.3, article p.104 · MOF structure optimization & DOS calculation · Fig. 4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated bandgap of PCN-700	4.19 eV	—	—	Text Exact Reported	main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Fig. 4

DFT geometry optimisation and PDOS with x/y-axial DHBQ linkers modelled as dianions.

Density functional theory

DFT reduced x/y-DHBQ linker saturated Ce-PCN-700-DHBQ model · Model

Chemical-environment/reduction variant of the linker-saturated Ce-PCN-700-DHBQ model.

Atmosphere: not_applicable
Geometry: periodic MOF model
Context: model_system
Measurement source: main p.10, article p.111 · Linker saturation · Fig. S5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Bandgap decrease upon chemical reduction of x/y-axial DHBQ linkers	decrease from 2.09 eV to 1.25 eV	—	—	Calculated From Reported Exact Reported	main p.10, article p.111 · Conclusion
Calculated bandgap of reduced linker saturated Ce-PCN-700-DHBQMarked as a best value within this paper	1.25 eV	—	—	Text Exact Reported	main p.10, article p.111 · Linker saturation · Fig. S5

Qualitative frontier-orbital component comparison from SI Table S2.

DFT linker saturated Ce-PCN-700-DHBQ model · Model

Compares PCN-700-DHBQ, Ce-PCN-700-DHBQ and linker-saturated Ce-PCN-700-DHBQ for whether continuous CT pathways are present in frontier orbitals.

Atmosphere: not_applicable
Geometry: periodic MOF model comparison
Context: model_system
Measurement source: SI pp.9-10 · Table S2 · Table S2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
SI Table S2 Ce-PCN-700-DHBQ frontier-orbital pathway status	Ce ions incorporated into the frontier, but frontier orbitals are still discontinuous at metal clusters due to oxygen atoms of metal-oxo units	—	—	SI Table Qualitative	SI p.9 · Table S2 · Table S2
SI Table S2 linker saturated Ce-PCN-700-DHBQ CT condition statusMarked as a best value within this paper	Conditions for long-range CT are now met	—	—	SI Table Qualitative	SI p.10 · Table S2 · Table S2
SI Table S2 PCN-700-DHBQ frontier-orbital pathway status	DHBQ pi-delocalised orbitals comprise frontier orbitals, but they are discontinuous	—	—	SI Table Qualitative	SI p.9 · Table S2 · Table S2

DFT geometry optimisation and PDOS for Ti-substituted M-PCN-700-DHBQ.

Density functional theory

DFT Ti-PCN-700-DHBQ model · Model

Ti4+ substituted for Zr4+ in PCN-700-DHBQ to lower metal energy levels and inspect LUCO composition.

Atmosphere: not_applicable
Geometry: periodic MOF model
Context: model_system
Measurement source: main p.7, article p.108 · Metal substitution · Fig. 5b; Fig. 6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated bandgap of Ti-PCN-700-DHBQ	2.39 eV	—	—	Text Exact Reported	main p.7, article p.108 · Metal substitution · Fig. 5b