Synthesis · Electrocatalytic Hydrogen Evolution from a Cobaloxime-Based Metal-Organic Framework Thin Film

5 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

S5 · Synthesis of bulk UU-100(Co) · Figures S4-S6

Metal precursorsZrCl4

Linker precursors[Co(dcpgH)(dcpgH2)]Cl2 cobaloxime linker

SolventsDMF

AdditivesGlacial acetic acid

Atmospherenot specified

Temperature80

Time120

Work-upAfter cooling, solid collected by filtration and washed with DMF (5 x 5 mL) and acetone (3 x 5 mL).

ActivationDried under vacuum for 12 h at room temperature.

Scalability context38 mg yellow solid from a 20 mL scintillation vial; longer ageing at 80C improved crystallinity, and 8 days gave satisfactory cRED data.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	26 mg, 0.11 mmol	S5 · Synthesis of bulk UU-100(Co) · Figures S4-S6
Linker	[Co(dcpgH)(dcpgH2)]Cl2	30 mg, 0.038 mmol	S5 · Synthesis of bulk UU-100(Co) · Figures S4-S6
Solvent	dimethylformamide (DMF)	8 mL	S5 · Synthesis of bulk UU-100(Co) · Figures S4-S6
Acid	glacial acetic acid	0.035 mL, 0.6 mmol	S5 · Synthesis of bulk UU-100(Co) · Figures S4-S6

Complete recipeSource: SI

Route 2: Other

S4-S5 · [Co(dcpgH)(dcpgH2)]Cl2

Metal precursorsCoCl2.4H2O

Linker precursors4,4'-dicarboxylic acid benzil dioxime (5)

SolventsAcetone; acetone/ether wash; ether wash

Atmosphereair

Temperatureroom temperature

Timeovernight

Work-upConcentrated to about 15 mL; precipitated yellow-brown solid collected by filtration; washed with cold acetone, 1:1 acetone/ether, and ether.

Scalability context0.4 g product, 51% yield; NMR showed about 20% minor product.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.4H2O	0.24 g, 1 mmol	S4-S5 · [Co(dcpgH)(dcpgH2)]Cl2
Linker	4,4'-dicarboxylic acid benzil dioxime (5)	0.66 g, 2 mmol	S4-S5 · [Co(dcpgH)(dcpgH2)]Cl2
Solvent	acetone	10 mL + 20 mL	S4-S5 · [Co(dcpgH)(dcpgH2)]Cl2

Complete recipeSource: SI

Route 3: Other

S4 · 4,4'-dicarboxylic acid benzil dioxime (5)

Linker precursorsBenzil-4,4'-dicarboxylic acid (4)

SolventsToluene; cold EtOH-Et2O mixture (3:1) for extraction

AdditivesHydroxylamine, 50 wt.% in water

Atmospherenot specified

Temperaturereflux

Timeovernight

Work-upSolvent removed under reduced pressure; residue extracted with cold EtOH-Et2O; filtered, washed with cold ethanol and ether, dried under vacuum.

Scalability context1.4 g product, 90% yield.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	benzil-4,4'-dicarboxylic acid (4)	1.4 g, 4.7 mmol	S4 · 4,4'-dicarboxylic acid benzil dioxime (5)
Additive	hydroxylamine, 50 wt.% in water	2.3 mL, 37 mmol, 8 equiv. · 50 wt.%	S4 · 4,4'-dicarboxylic acid benzil dioxime (5)
Solvent	toluene	75 mL	S4 · 4,4'-dicarboxylic acid benzil dioxime (5)

Complete recipeSource: Both

Route 4: Solvothermal

S16-S17 · Preparation of UU-100(Co)|FTO thin film

Metal precursorsZrCl4

Linker precursors[Co(dcpgH)(dcpgH2)]Cl2 cobaloxime linker

SolventsDMF

AdditivesGlacial acetic acid; cobaloxime SAM on FTO

Atmospherenot specified

Temperature80

Time120

Substrate orientationSingle SAM-coated FTO slide placed in vial with conductive side facing down.

Work-upWashed with DMF and stored in DMF; before use sonicated in DMF for 10 s, soaked in acetone for 1 min, dried in air.

ActivationBrief acetone soak and air drying immediately before use.

Scalability contextFTO slides cut to 2 x 1 cm2; one slide per 20 mL vial.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	FTO slide	2 x 1 cm2 slide · 7 ohm/sq	S16-S17 · Preparation of UU-100(Co)\|FTO thin film
Metal Source	ZrCl4	26 mg, 0.11 mmol	S16-S17 · Preparation of UU-100(Co)\|FTO thin film
Linker	cobaloxime linker 6	30 mg, 0.038 mmol · 1 mM for SAM step	S16-S17 · Preparation of UU-100(Co)\|FTO thin film
Solvent	DMF	8 mL	S16-S17 · Preparation of UU-100(Co)\|FTO thin film
Acid	glacial acetic acid	0.035 mL, 0.6 mmol	S16-S17 · Preparation of UU-100(Co)\|FTO thin film

Complete recipeSource: Both

Route 5: Solvothermal

S17 · Synthesis of UU-100(Co)|GC thin film

Metal precursorsZrCl4 preassembled with acetic acid

Linker precursors[Co(dcpgH)(dcpgH2)]Cl2 cobaloxime linker

SolventsDMF; acetonitrile for diazonium electrografting

Additives(4-carboxy)benzene diazonium tetrafluoroborate; tetrabutylammonium tetrafluoroborate; glacial acetic acid

Atmospherenot specified

Temperature80

Time120

Substrate orientationSingle carboxylic-acid-functionalised GC plate placed in vial.

Oxidant / reductantElectrografting by CV reduction of diazonium salt, two cycles at 50 mV/s between 0.0 and -1.4 V vs Fc+/0.

Work-upElectrode washed with DMF and stored in DMF; briefly dipped in acetone twice for less than 5 s before PXRD.

ActivationBrief acetone dips before recording as-synthesised PXRD.

Scalability contextOne functionalised GC plate per 20 mL vial; geometric electrode area used for HER was 0.5 cm2.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	glassy carbon plate	single plate	S17 · Synthesis of UU-100(Co)\|GC thin film
Other	(4-carboxy)benzene diazonium tetrafluoroborate	4 mg, 0.015 mmol	S17 · Synthesis of UU-100(Co)\|GC thin film
Electrolyte	tetrabutylammonium tetrafluoroborate	0.1 M in acetonitrile	S17 · Synthesis of UU-100(Co)\|GC thin film
Metal Source	ZrCl4	26 mg	S17 · Synthesis of UU-100(Co)\|GC thin film
Linker	cobaloxime linker 6	30 mg	S17 · Synthesis of UU-100(Co)\|GC thin film
Acid	acetic acid	0.035 mL	S17 · Synthesis of UU-100(Co)\|GC thin film
Solvent	DMF	8 mL	S17 · Synthesis of UU-100(Co)\|GC thin film