Electrical Transport — Experimental manifestation of redox-conductivity in metal-organic frameworks and its implication for semiconductor/insulator switching

6 measurement groups · 24 results

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

CV and EIS-derived redox conductivity

Electrical conductivity Impedance spectroscopy Voltammetry

UU-100(Co) thin film on FTO · Thin Film

Representative CV at 100 mV s-1 and EIS conductivity analysis in Ar-saturated DMF with 0.1 M KPF6.

Atmosphere: Ar-saturated
Geometry: FTO-supported thin film in electrochemical cell.
Context: Pristine UU-100(Co) thin film, x = 0.0 to 1.0.
Measurement source: 6 · Generality of the redox conductivity with other MOFs · Fig. 4f; Supplementary Figs. 30-32

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
UU-100(Co) redox-conductivity peak potential	-1.19 V vs Ag/AgNO3	—	—	Text Exact Reported	6 · Generality of the redox conductivity with other MOFs · Fig. 4f
UU-100(Co) maximum redox conductivityMarked as a best value within this paper	approximately 0.07 uS cm-1 from Fig. 4f	7e-8 S cm-1	visual estimate from plotted right y-axis	Figure Axis Approximate	6 · Figure 4 · Fig. 4f

Countercation-dependent CV and EIS redox conductivity

Electrical conductivity Impedance spectroscopy Voltammetry

Zn(pyrazol-NDI) thin film on FTO · Thin Film

CV at 5 mV s-1 and steady-state redox conductivity in Ar-saturated DMF with 0.1 M KPF6, LiClO4, or TBAPF6.

Atmosphere: Ar-saturated
Geometry: FTO-supported Zn(pyrazol-NDI) thin film in electrochemical cell.
Context: Pristine Zn(pyrazol-NDI) thin film measured with different electrolyte cations.
Measurement source: 6-7 · Counter cation dependent redox conductivity · Fig. 5; Supplementary Figs. 33-42

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Activation barrier for 0.5-Zn(pyrazol-NDI) with Li+	150 meV	—	—	Text Exact Reported	7 · Counter cation dependent redox conductivity · Supplementary Fig. 42a
Activation barrier for 0.5-Zn(pyrazol-NDI) with TBA+	142 meV	—	—	Text Exact Reported	7 · Counter cation dependent redox conductivity · Supplementary Fig. 42b
Maximum redox conductivity of 0.5-Zn(pyrazol-NDI) with K+Marked as a best value within this paper	7.1 uS cm-1	0.0000071 S cm-1	—	Text Exact Reported	7 · Counter cation dependent redox conductivity · Fig. 5a; Fig. 3b
Maximum redox conductivity of 0.5-Zn(pyrazol-NDI) with Li+	1.2 uS cm-1	0.0000012 S cm-1	—	Text Exact Reported	7 · Counter cation dependent redox conductivity · Fig. 5b
Maximum redox conductivity of 0.5-Zn(pyrazol-NDI) with TBA+	3.9 uS cm-1	0.0000039 S cm-1	—	Text Exact Reported	7 · Counter cation dependent redox conductivity · Fig. 5c

Electrochemical impedance spectroscopy-derived redox conductivity

Electrical conductivity Impedance spectroscopy

Zn(pyrazol-NDI) thin film on FTO · Thin Film

Thin films preconditioned at desired applied potentials for 2 min by chronoamperometry; EIS with 10 mV AC modulation from 0.1 to 10000 Hz in Ar-saturated DMF with 0.1 M KPF6; resistance from RC equivalent circuit converted to conductivity by Ohm's law.

Atmosphere: Ar-saturated
Geometry: MOF thin-film working electrode on FTO in three-electrode electrochemical cell; conductivity calculated using film thickness and measurement area.
Context: Pristine Zn(pyrazol-NDI) thin film modulated over x = 0.0 to 2.0.
Measurement source: 4,8 · Redox state dependent conductivity; Methods · Fig. 3a,b; Supplementary Figs. 8-12

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
EIS AC potential modulation	10 mV	0.01 V	—	Text Exact Reported	8 · Methods: Redox conductivity and activation energy measurements
EIS frequency range	0.1-10,000 Hz	—	—	Text Exact Reported	8 · Methods: Redox conductivity and activation energy measurements
Redox-state preconditioning time before EIS	2 minutes / 120 s	2 min	—	Text Exact Reported	4 · Redox state dependent conductivity · Fig. 3 caption
Conductivity enhancement in mixed-redox Zn(pyrazol-NDI)	10000-fold higher in x = 0.5 or 1.5 than x = 0.0 or 2.0	—	—	Text Rounded Reported	4 · Redox state dependent conductivity · Fig. 3b
Zn(pyrazol-NDI) low-state redox conductivity range	10^-10 to 10^-9 S cm-1 for x = 0.0 or x = 2.0	—	—	Text Range	4 · Redox state dependent conductivity · Fig. 3b
Zn(pyrazol-NDI) mixed-redox maximum conductivity range	10^-5 to 10^-6 S cm-1	—	—	Text Range	4 · Redox state dependent conductivity · Fig. 3b
Maximum redox conductivity of 1.5-Zn(pyrazol-NDI) with K+	approximately 6 uS cm-1 from Fig. 3b blue Gaussian peak	0.000006 S cm-1	visual estimate from plotted axis	Figure Axis Approximate	5 · Figure 3 · Fig. 3b

Repeated redox-conductivity switching by EIS

Electrical conductivity Impedance spectroscopy

Zn(pyrazol-NDI) thin film on FTO · Thin Film

Redox conductivity switched between x = 0.0 and x = 0.5 over 100 cycles, about 24 h operation.

Atmosphere: Ar-saturated
Geometry: FTO-supported MOF thin film in electrochemical EIS cell.
Context: Pristine Zn(pyrazol-NDI) thin film.
Measurement source: 4-5 · Redox state dependent conductivity · Fig. 3d; Supplementary Fig. 13

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Zn(pyrazol-NDI) CV peak loss after 100 CV cycles	~2.7% loss after 100 cycles of CV	—	~	Caption Approximate	15 · Redox switchability and structural stability · Supplementary Fig. 14
Zn(pyrazol-NDI) redox conductivity switching cyclesMarked as a best value within this paper	100 cycles (~24 h operation)	—	—	Caption Exact Reported	5 · Figure 3 caption · Fig. 3d
CV redox-wave shift after redox conductivity cycling	~20 mV anodic shift	0.02 V	~	Caption Approximate	14 · Redox switchability and structural stability · Supplementary Fig. 13
Estimated Zn(pyrazol-NDI) film loss after redox conductivity cycling	~15% loss according to first reduction peak	—	~	Caption Approximate	14 · Redox switchability and structural stability · Supplementary Fig. 13

Variable-temperature EIS Arrhenius analysis

Impedance spectroscopy

0.5-Zn(pyrazol-NDI), KPF6 electrolyte · Thin Film

Variable-temperature EIS on neutral 0.0-Zn(pyrazol-NDI) and mixed-valent 0.5-Zn(pyrazol-NDI); fitted to Arrhenius-type relation.

Temperature: temperature varied; exact range not reported in text
Atmosphere: Ar-saturated electrochemical cell
Geometry: FTO-supported thin-film electrochemical cell with temperature controlled by chiller/isopropanol.
Context: Pristine Zn(pyrazol-NDI) redox states.
Measurement source: 4 · Redox state dependent conductivity · Fig. 3c

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Activation barrier for 0.5-Zn(pyrazol-NDI) with K+Marked as a best value within this paper	40.4 meV (0.93 kcal mol-1)	—	—	Text Exact Reported	4 · Redox state dependent conductivity · Fig. 3c
Activation barrier for 0.0-Zn(pyrazol-NDI) with K+	82.9 meV (1.91 kcal mol-1)	—	—	Text Exact Reported	4 · Redox state dependent conductivity · Fig. 3c

CV and EIS-derived redox conductivity

Electrical conductivity Impedance spectroscopy Voltammetry

Zr(dcphOH-NDI) thin film on FTO · Thin Film

Representative CV at 100 mV s-1 and EIS conductivity analysis in Ar-saturated DMF with 0.1 M KPF6.

Atmosphere: Ar-saturated
Geometry: FTO-supported thin film in electrochemical cell.
Context: Pristine Zr(dcphOH-NDI) thin film, x = 0.0 to 2.0.
Measurement source: 6 · Generality of the redox conductivity with other MOFs · Fig. 4c; Supplementary Figs. 22-25

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Zr(dcphOH-NDI) first redox-conductivity peak potential	-1.05 V vs Ag/AgNO3	—	—	Text Exact Reported	6 · Generality of the redox conductivity with other MOFs · Fig. 4c
Zr(dcphOH-NDI) second redox-conductivity peak potential	-1.29 V vs Ag/AgNO3	—	—	Text Exact Reported	6 · Generality of the redox conductivity with other MOFs · Fig. 4c
Zr(dcphOH-NDI) maximum redox conductivity at first redox peak	approximately 0.30 uS cm-1 from Fig. 4c	3e-7 S cm-1	visual estimate from plotted right y-axis	Figure Axis Approximate	6 · Figure 4 · Fig. 4c
Zr(dcphOH-NDI) maximum redox conductivity at second redox peakMarked as a best value within this paper	approximately 0.45 uS cm-1 from Fig. 4c	4.5e-7 S cm-1	visual estimate from plotted right y-axis	Figure Axis Approximate	6 · Figure 4 · Fig. 4c