Synthesis · Discovery of Dual Ion-Electron Conductivity of Metal-Organic Frameworks via Machine Learning-Guided Experimentation

3 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: Main

Route 1: Solvothermal

1146 · 3.1.1. Synthesis of 1

Metal precursorsCu(NO3)2.3H2O (0.2898 g, 1.2 mmol)

Linker precursors1H-pyrazole-4-carboxylic acid (H2L) (0.2016 g, 1.8 mmol)

Solvents12.0 mL DMF, 9.0 mL deionized water, 12.0 mL ethanol

Atmosphereautogenous pressure in Teflon-lined pressure vessel

Temperature80

Time72

Work-upCool to room temperature; dark blue crystals washed with DI water and filtered under vacuum.

ActivationFor activated samples: 80 deg C for 15 h; main text does not specify vacuum/gas details beyond removal of residual moisture.

Scalability contextConclusion notes broader synthesis challenges: limited literature, discontinued precursors, low yields, intricate ligand synthesis, toxic chemicals and prolonged drying.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1H-pyrazole-4-carboxylic acid (H2L)	0.2016 g, 1.8 mmol	1146 · 3.1.1. Synthesis of 1
Metal Source	Cu(NO3)2.3H2O	0.2898 g, 1.2 mmol	1146 · 3.1.1. Synthesis of 1
Solvent	DMF	12.0 mL	1146 · 3.1.1. Synthesis of 1
Solvent	deionized water	9.0 mL	1146 · 3.1.1. Synthesis of 1
Solvent	ethanol	12.0 mL	1146 · 3.1.1. Synthesis of 1

Partial recipeSource: Main

Route 2: Other

1146 · 3.1.2. Synthesis of 2

Metal precursorsCu(NO3)2.3H2O (0.976 g, 4 mmol)

Linker precursors1H-pyrazole-4-carboxylic acid (H2L) (0.456 g, 4 mmol)

Solvents60 mL solution of 15:1 aqueous ammonia

Additivesaqueous ammonia

Atmosphereambient atmosphere not otherwise specified

Temperatureroom temperature

Time72

Work-upCrystals rinsed with DI water and filtered under vacuum to separate them from remaining liquid.

ActivationFor activated samples: 80 deg C for 15 h; main text does not specify vacuum/gas details beyond removal of residual moisture.

Scalability contextConclusion notes broader synthesis challenges: limited literature, discontinued precursors, low yields, intricate ligand synthesis, toxic chemicals and prolonged drying.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H2L	0.456 g, 4 mmol	1146 · 3.1.2. Synthesis of 2
Metal Source	Cu(NO3)2.3H2O	0.976 g, 4 mmol	1146 · 3.1.2. Synthesis of 2
Solvent	15:1 aqueous ammonia solution	60 mL	1146 · 3.1.2. Synthesis of 2
Base	aqueous ammonia	component of 60 mL 15:1 solution	1146 · 3.1.2. Synthesis of 2

Complete recipeSource: SI

Route 3: Drop Cast

S11 · Working Electrode Preparation for Cyclic Voltammetry · Figures S9-S10

Solvents1000 uL EtOH plus 120 uL 5% w/v PEG solution; 20 uL acetic anhydride

AdditivesPEG binder, acetic anhydride

Atmospheresolutions purged with pure nitrogen for 30 min; nitrogen blanket during measurement

Temperatureroom temperature

Time0.5

Substrate orientationglassy carbon electrode tip

Work-upSlurry sonicated for 30 min, then 40 uL deposited on clean dry glassy carbon electrode; electrode re-polished between samples.

Scalability contextMeasurement preparation only, not bulk MOF synthesis.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	powdered MOF	30 mg	S11 · Working Electrode Preparation for Cyclic Voltammetry · Figures S9-S10
Additive	PEG in EtOH	120 uL of 5% PEG · 5% w/v	S11 · Working Electrode Preparation for Cyclic Voltammetry · Figures S9-S10
Solvent	EtOH	1000 uL	S11 · Working Electrode Preparation for Cyclic Voltammetry · Figures S9-S10
Additive	acetic anhydride	20 uL	S11 · Working Electrode Preparation for Cyclic Voltammetry · Figures S9-S10