Synthesis · Ligand-Oxidation-Based Anodic Synthesis of Oriented Films of Conductive M-Catecholate Metal-Organic Frameworks with Controllable Thickness

8 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Electrochemical

SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S31

Metal precursorsCo(Ac)2 (2.25 mM); SI chemicals list specifies Co(Ac)2.4H2O.

Linker precursorsHHTP (1.125 mM)

Solventsn-propanol/H2O (v/v 1:1.5)

AdditivesHAc (2.4 mM); NaCl (100 mM)

AtmospherePrecursor freshly prepared and purged with nitrogen for 30 min.

Temperature30

Time1 for Fig. S31 sample (60 min)

Substrate orientationAu working electrode; FTO counter; Ag/AgCl reference.

Oxidant / reductantAnodic ligand oxidation at 0.30 V.

Work-upRinsed with DMF and methanol; dried under nitrogen flow.

ActivationNot reported.

Scalability contextGenerality demonstration only.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(Ac)2	2.25 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S31
Linker	HHTP	1.125 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S31
Acid	HAc	2.4 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S31
Electrolyte	NaCl	100 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S31
Solvent	n-propanol/H2O	v/v 1:1.5	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S31

Complete recipeSource: Both

Route 2: Electrochemical

SI p.3 · Anodic deposition of M-catecholate MOF films

Metal precursorsCu(NO3)2 (2.25 mM); SI chemicals list specifies Cu(NO3)2.3H2O.

Linker precursorsHHTP (1.125 mM)

SolventsDMF/H2O (v/v 1:15)

AdditivesHNO3 (0.5 mM); NaCl (100 mM) supporting electrolyte

AtmosphereNitrogen-saturated precursor solution; deposition under nitrogen atmosphere after 30 min N2 purge.

Temperature30

TimeDesired time; main Figure 2 sample used 45 min (0.75 h).

Substrate orientationAu, silicon, ITO, FTO or freshly peeled HOPG working electrode; FTO counter; Ag/AgCl reference.

Oxidant / reductantAnodic oxidation of redox-active HHTP catechol ligand at 0.25-0.35 V versus Ag/AgCl.

Work-upRinsed with DMF and methanol; dried under nitrogen flow.

ActivationFor gas sorption only: evacuated under vacuum at 100 C for 24 h.

Scalability contextMain text states the approximately 2.5 x 2.5 cm2 film area can be increased using a larger electrode.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2; Cu(NO3)2.3H2O listed in chemicals	2.25 mM	SI p.3 · Anodic deposition of M-catecholate MOF films
Linker	HHTP	1.125 mM	SI p.3 · Anodic deposition of M-catecholate MOF films
Acid	HNO3	0.5 mM	SI p.3 · Anodic deposition of M-catecholate MOF films
Electrolyte	NaCl	100 mM	SI p.3 · Anodic deposition of M-catecholate MOF films
Solvent	DMF/H2O	v/v 1:15	SI p.3 · Anodic deposition of M-catecholate MOF films

Complete recipeSource: Both

Route 3: Electrochemical

SI p.4 · Device fabrication and conductivity measurement · Fig. S25

Metal precursorsCu(NO3)2-based Cu3(HHTP)2 anodic precursor solution as above.

Linker precursorsHHTP

SolventsDMF/H2O precursor solvent; I2/KI aqueous etchant used after deposition.

AdditivesHNO3, NaCl in precursor; I2/KI etching solution; Au evaporated contacts.

AtmosphereNitrogen-purged precursor for deposition; electrical measurement under ~10^-5 mbar vacuum.

Temperature30 for deposition; transport measured 100-300 K

TimeNot specified for achieving ~100 nm film.

Substrate orientationAu (40 nm) pre-coated silica glass slide without Cr adhesive layer; final film stacked on silica after Au removal.

Oxidant / reductantAnodic ligand oxidation during film deposition; iodine/iodide chemical etching of underlying Au.

Work-upUnderlying Au etched in I2/KI aqueous solution; four 40 nm Au contacts evaporation-deposited through a shadow mask.

ActivationNo gas-sorption activation; transport measured under vacuum.

Scalability contextFour-probe geometry: L 100 um, W 9000 um, d 100 nm.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Au pre-coated silica glass slide	40 nm Au	SI p.4 · Device fabrication and conductivity measurement · Fig. S25
Oxidant	I2/KI aqueous solution	Not specified	SI p.4 · Device fabrication and conductivity measurement · Fig. S25
Other	Au contact electrodes	40 nm thickness	SI p.4 · Device fabrication and conductivity measurement · Fig. S25

Partial recipeSource: Both

Route 4: Electrochemical

main p.6, article p.25575 · Results and Discussion · Fig. 6

Metal precursorsCu(NO3)2-based Cu3(HHTP)2 anodic precursor solution as above.

Linker precursorsHHTP

SolventsDMF/H2O precursor solution; solvent for PCTE removal not specified in text.

AdditivesHNO3 and NaCl in precursor.

AtmosphereNitrogen-purged precursor / nitrogen atmosphere as for anodic deposition.

Temperature30

TimeNot specified for nanorod growth.

Substrate orientationAu-coated PCTE membrane template; pore diameter 200 nm, membrane thickness 10 um.

Oxidant / reductantAnodic ligand oxidation confined in porous PCTE template.

Work-upPCTE template removed by dissolution to release nanorods.

ActivationNot reported.

Scalability contextTemplate converts continuous film growth to high-aspect-ratio nanorods.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Au-coated PCTE membrane	200 nm pore diameter; 10 um thickness	main p.6, article p.25575 · Results and Discussion · Fig. 6
Metal Source	Cu(NO3)2	2.25 mM	main p.6, article p.25575 · Results and Discussion · Fig. 6
Linker	HHTP	1.125 mM	main p.6, article p.25575 · Results and Discussion · Fig. 6

Complete recipeSource: SI

Route 5: Solvothermal

SI p.3 · Solvothermal synthesis of Cu3(HHTP)2 film · Fig. S7

Metal precursorsCopper acetate monohydrate (80 mg, 0.4 mmol)

Linker precursorsHHTP (65 mg, 0.2 mmol)

Solvents10 mL water/DMF (v/v 1:1)

AdditivesNone reported.

AtmosphereNot specified.

Temperature85

Time18

Substrate orientationAu-coated glass substrate placed face-down in solution.

Oxidant / reductantNot specified; solvothermal coordination growth.

Work-upAfter cooling, rinsed with DMF and methanol; dried under nitrogen flow.

ActivationNot reported.

Scalability contextLiterature control route; no scale-up claim in this work.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate monohydrate	80 mg, 0.4 mmol	SI p.3 · Solvothermal synthesis of Cu3(HHTP)2 film · Fig. S7
Linker	HHTP	65 mg, 0.2 mmol	SI p.3 · Solvothermal synthesis of Cu3(HHTP)2 film · Fig. S7
Solvent	water/DMF	10 mL · v/v 1:1	SI p.3 · Solvothermal synthesis of Cu3(HHTP)2 film · Fig. S7

Complete recipeSource: SI

Route 6: Electrochemical

SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S37

Metal precursorsCu(NO3)2 (2.25 mM)

Linker precursors8OH-TBA (1.125 mM)

SolventsDMF/H2O (v/v 1:1.5)

AdditivesHNO3 (0.75 mM); NaCl (100 mM)

AtmospherePrecursor freshly prepared and purged with nitrogen for 30 min.

Temperature30

Time1 for Fig. S37 sample (60 min)

Substrate orientationAu working electrode; FTO counter; Ag/AgCl reference.

Oxidant / reductantAnodic oxidation of TBA catechol ligand at 0.30 V.

Work-upRinsed with DMF and methanol; dried under nitrogen flow.

ActivationNot reported.

Scalability contextGenerality demonstration with an alternate catechol linker.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2	2.25 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S37
Linker	8OH-TBA	1.125 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S37
Acid	HNO3	0.75 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S37
Electrolyte	NaCl	100 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S37
Solvent	DMF/H2O	v/v 1:1.5	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S37

Complete recipeSource: SI

Route 7: Electrochemical

SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S34

Metal precursorsYb(NO3)3 (90 mM); SI chemicals list specifies Yb(NO3)3.5H2O.

Linker precursorsHHTP (2.16 mM)

SolventsDMI/H2O (v/v 1:20)

AdditivesHNO3 (0.4 mM)

AtmospherePrecursor freshly prepared and purged with nitrogen for 30 min.

Temperature30

Time1 for Fig. S34 sample (60 min)

Substrate orientationAu working electrode; FTO counter; Ag/AgCl reference.

Oxidant / reductantAnodic ligand oxidation at 0.25 V.

Work-upRinsed with DMF and methanol; dried under nitrogen flow.

ActivationNot reported.

Scalability contextGenerality demonstration only.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Yb(NO3)3	90 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S34
Linker	HHTP	2.16 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S34
Acid	HNO3	0.4 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S34
Solvent	DMI/H2O	v/v 1:20	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S34

Complete recipeSource: SI

Route 8: Electrochemical

SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S28

Metal precursorsZn(Ac)2 (2.25 mM); SI chemicals list specifies Zn(Ac)2.2H2O.

Linker precursorsHHTP (1.125 mM)

Solventsn-propanol/H2O (v/v 1:1.5)

AdditivesHAc (2.4 mM); NaCl (100 mM)

AtmospherePrecursor freshly prepared and purged with nitrogen for 30 min.

Temperature30

Time0.5 for Fig. S28 sample (30 min)

Substrate orientationAu working electrode; FTO counter; Ag/AgCl reference.

Oxidant / reductantAnodic ligand oxidation at 0.30 V.

Work-upRinsed with DMF and methanol; dried under nitrogen flow.

ActivationNot reported.

Scalability contextGenerality demonstration only.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(Ac)2	2.25 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S28
Linker	HHTP	1.125 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S28
Acid	HAc	2.4 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S28
Electrolyte	NaCl	100 mM	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S28
Solvent	n-propanol/H2O	v/v 1:1.5	SI p.3 · Anodic deposition of M-catecholate MOF films · Fig. S28