Computational Modelling — Air-Stability and Carrier Type in Conductive M3(Hexaaminobenzene)2,(M = Co, Ni, Cu)

Measurement evidence

Computational Modelling

Air-Stability and Carrier Type in Conductive M3(Hexaaminobenzene)2,(M = Co, Ni, Cu) · Hinckley A.C., Park J., Gomes J. et al. · Journal of the American Chemical Society · 2020 · 11123-11130

2 measurement groups · 31 results

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

B3LYP-D2/6-31G* fragment charge-transfer analysis using absolutely localized molecular orbitals in Q-Chem 4.3

Ni-HAB DFT model · Model

M(HAB)2 and M(OPD)2 fragment models for M = Co, Ni, Cu

Atmosphere: computational
Context: fragment model systems
Measurement source: S5 · Computational details · Table 2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co(HAB)2 metal-to-ligand back-bonding charge transfer	DeltaQ[M->L] = 0.167 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Co(HAB)2 forward ligand-to-metal charge donation	DeltaQ[L->M] = 0.178 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Co(HAB)2 net charge transfer	DeltaQ = 0.0112 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Co(OPD)2 net charge transfer	DeltaQ = 0.145 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Cu(HAB)2 metal-to-ligand back-bonding charge transfer	DeltaQ[M->L] = 0.810 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Cu(HAB)2 forward ligand-to-metal charge donation	DeltaQ[L->M] = 2.09 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Cu(HAB)2 net charge transfer	DeltaQ = 1.28 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Cu(OPD)2 net charge transfer	DeltaQ = 0.860 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Ni(HAB)2 metal-to-ligand back-bonding charge transfer	DeltaQ[M->L] = 0.100 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Ni(HAB)2 forward ligand-to-metal charge donation	DeltaQ[L->M] = 0.0935 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Ni(HAB)2 net charge transfer	DeltaQ = -0.00685 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2
Ni(OPD)2 net charge transfer	DeltaQ = -0.450 e-	—	—	Table Exact Reported	11127 · Experimental determination of electronic structure · Table 2

DFT+U band structure and density of states; PBE functional, D2 dispersion, PAW, Quantum Espresso 6.2, U=5 and J=1

Density functional theory

Co-HAB DFT model · Model

Hexagonal unit cell, a=b=13.2 Angstrom, c/interlayer spacing 3.2 Angstrom, 39 atoms per periodic box

Atmosphere: computational
Context: model systems for all M-HABs; result rows specify material
Measurement source: S5 · Computational details · Table 1; Figure S1; Figure S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HAB calculated bandgap	0.25 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Co-HAB conduction bandwidth	0.106 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Co-HAB valence bandwidth	0.077 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Co-HAB calculated electron effective mass	0.538 me	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Co-HAB calculated hole effective mass	2.66 me	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Co-HAB calculated electron mobility near 35 degC	approximately 0.25 cm2 V-1 s-1	—	—	Figure Axis Approximate	11126 · Results and Discussion · Figure 3A
Cu-HAB calculated bandgap	0.47 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Cu-HAB conduction bandwidth	0.111 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Cu-HAB valence bandwidth	0.060 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Cu-HAB calculated electron effective mass	0.678 me	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Cu-HAB calculated hole effective mass	1.35 me	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Cu-HAB calculated electron mobility near 35 degC	approximately 0.014 cm2 V-1 s-1	—	—	Figure Axis Approximate	11128 · Conclusion · Figure 3A
Ni-HAB calculated bandgap	0.49 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Ni-HAB conduction bandwidth	0.051 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Ni-HAB valence bandwidth	0.071 eV	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Ni-HAB calculated electron effective mass	0.829 me	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Ni-HAB calculated hole effective mass	1.40 me	—	—	Table Exact Reported	11126 · Results and Discussion · Table 1
Ni-HAB calculated electron mobility near 35 degCMarked as a best value within this paper	approximately 1.0 cm2 V-1 s-1	—	—	Figure Axis Approximate	11126 · Results and Discussion · Figure 3A
Metal contribution to M-HAB conduction bands from PDOS	zero complete states from the metal; carriers predominantly located on ligand	—	—	Text Qualitative	11127 · Experimental determination of electronic structure · Figure S4