Synthesis · Does the Mode of Metal-Organic Framework/Electrode Adhesion Determine Rates for Redox-Hopping-Based Charge Transport within Thin-Film Metal-Organic Frameworks?

4 structured synthesis routes

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

Vague recipeSource: Main

Route 1: Solvothermal

4 · Results and Discussion

Metal precursorsnot specified in assigned documents; follows ref 71

Linker precursorsnot specified in assigned documents; follows ref 71

Solventsnot specified in assigned documents

Additivesnot specified in assigned documents

Atmospherenot specified

Temperaturenot specified

Timenot specified

Substrate orientationnone; bulk powder

Oxidant / reductantnone reported

Work-upnot specified

Activationnot specified

Scalability contextUsed only as bulk-composition comparison; exact cited external recipe not required for thin-film transport extraction.

Partial recipeSource: Main

Route 2: Electrochemical

3 · Experimental Section

Metal precursorspreformed acid-treated MOF-525 powder containing Zr nodes

Linker precursorspreformed acid-treated MOF-525 powder containing TCPP linkers

Solventstoluene

Additivesnone reported

Atmospherenot specified; fume hood safety note

Temperatureroom temperature implied but not specified

Time15 min deposition; air-dried 24 h

Substrate orientationtwo FTO electrodes spaced 1 cm apart; resulting films deposited on the cathode

Oxidant / reductantDC voltage of 120 V applied across FTO electrodes

Work-upfilms deposited on cathode; all samples air-dried for 24 h

Activationuses acid-treated MOF-525 powder precursor

Scalability contextSafety note: toluene can be ignited by sparks; small-area electrodes and slotted spacer used.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	acid-treated MOF-525 powder	10 mg	3 · Experimental Section
Solvent	toluene	Not specified	3 · Experimental Section
Other	FTO electrode	two electrodes spaced 1 cm apart	3 · Experimental Section
Other	DC voltage	120 V for 15 min	3 · Experimental Section

Partial recipeSource: Main

Route 3: Solvothermal

3 · Experimental Section

Metal precursorszirconyl chloride octahydrate

Linker precursorsTCPP

SolventsDMF; acetone

Additivesbenzoic acid; aqueous 8 M HCl

Atmospherenot specified

Temperaturenot specified in assigned documents

Timenot specified; all samples air-dried 24 h

Substrate orientationnone; excess powder from solvothermal film synthesis

Oxidant / reductantnone reported

Work-upacid aqueous solution (26:1 DMF/aq. 8 M HCl) to remove residual modulator/starting material; solvent exchange with acetone; air-dried 24 h

Activationacid treatment in 26:1 DMF/aqueous 8 M HCl followed by acetone exchange

Scalability contextPowder was excess material from film growth and used to minimise batch variation for EPD films.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconyl chloride octahydrate	Not specified	3 · Experimental Section
Linker	TCPP	Not specified	3 · Experimental Section
Solvent	DMF	Not specified	3 · Experimental Section
Acid	aqueous HCl	8 M	3 · Experimental Section
Additive	benzoic acid	Not specified	3 · Experimental Section
Solvent	acetone	Not specified	3 · Experimental Section

Partial recipeSource: Main

Route 4: Solvothermal

3 · Experimental Section

Metal precursorszirconyl chloride octahydrate (Alfa Aesar, 99.9%)

Linker precursorsmeso-tetra(4-carboxyphenyl)porphine (TCPP, Frontier Scientific, >97%)

SolventsDMF; acetone for solvent exchange

Additivesbenzoic acid modulator; aqueous 8 M HCl in DMF/acid treatment solution

Atmospherenot specified

Temperaturenot specified in assigned documents; procedure cited to prior work

Timenot specified for solvothermal growth; air-dried 24 h after film preparation

Substrate orientationFTO conductive glass electrode; directly grown electrode-attached ST form

Oxidant / reductantnone reported

Work-upacid solution used to remove residual nonligated benzoic acid and starting material; 100:1 DMF/acid solution for electrode-attached ST form; solvent exchange with acetone; all samples air-dried 24 h

Activationacid treatment/activation in 100:1 DMF/aqueous 8 M HCl followed by acetone solvent exchange

Scalability contextDirect solvothermal film growth on FTO; exact solvothermal conditions deferred to cited ref 74, not reproduced here.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconyl chloride octahydrate	Not specified	3 · Experimental Section
Linker	meso-tetra(4-carboxyphenyl)porphine (TCPP)	Not specified	3 · Experimental Section
Solvent	N,N-dimethylformamide (DMF)	Not specified	3 · Experimental Section
Additive	benzoic acid	Not specified	3 · Experimental Section
Acid	aqueous HCl	8 M	3 · Experimental Section
Solvent	acetone	Not specified	3 · Experimental Section