Synthesis · Bromo- and iodo-bridged building units in metal-organic frameworks for enhanced carrier transport and CO2 photoreduction by water vapor

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

10 · Synthesis of [Pb(NH2-bdc)]n

Metal precursorsPb(NO3)2, 0.083 g (0.25 mmol)

Linker precursors2-aminoterephthalic acid, 0.042 g (0.25 mmol)

Solvents2 mL DMF

Atmospheresealed Teflon-lined autoclave in stainless-steel vessel; atmosphere not otherwise specified

Temperature120

Time48

Work-upCool to room temperature; isolate yellow crystals by vacuum filtration and rinse with EtOH.

Scalability contextYield 0.078 g, 81% based on total Pb.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Pb(NO3)2	0.083 g; 0.25 mmol	10 · Synthesis of [Pb(NH2-bdc)]n
Linker	2-aminoterephthalic acid	0.042 g; 0.25 mmol	10 · Synthesis of [Pb(NH2-bdc)]n
Solvent	DMF	2 mL	10 · Synthesis of [Pb(NH2-bdc)]n

Complete recipeSource: Both

Route 2: Other

10 · Synthesis of ultrasmall Ru NPs · Supplementary Fig. 53

Metal precursorsRu3(CO)12, 25 mg (0.039 mmol)

Solvents8 mL tri-n-octylamine; final dispersion in toluene

AtmosphereDegassed for 30 min at room temperature, then flushed with nitrogen

Temperature270

Time0.5

Oxidant / reductantthermal decomposition of Ru3(CO)12

Work-upWash particles with EtOH twice; isolate by centrifugation at 8500 rpm for 3 min; disperse in toluene.

Scalability contextFinal colloidal Ru NP concentration approximately 1 mg/mL.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ru3(CO)12	25 mg; 0.039 mmol	10 · Synthesis of ultrasmall Ru NPs · Supplementary Fig. 53
Solvent	tri-n-octylamine (TOA)	8 mL	10 · Synthesis of ultrasmall Ru NPs · Supplementary Fig. 53
Solvent	toluene	final dispersion · approximately 1 mg/mL Ru NPs	10 · Synthesis of ultrasmall Ru NPs · Supplementary Fig. 53

Complete recipeSource: Both

Route 3: Other

10 · Synthesis of Ru@TMOF-10-NH2(I)

Metal precursorspreformed Ru NP solution, 0.2-1 mL

Solvents10 mL DMF; EtOH wash

Additives60 mg as-prepared TMOF-10-NH2(I)

Atmosphereambient room-temperature incubation; atmosphere not specified

Temperatureroom temperature, then 60 °C vacuum drying

Time12 h incubation; 30 min sonication; overnight vacuum drying

Work-upCentrifuge at 5500 rpm for 2 min; wash with EtOH three times; dry under vacuum at 60 °C overnight.

ActivationComposite dried under vacuum at 60 °C overnight.

Scalability contextRu:DMF v/v ratios 2.0, 4.8 and 9.1% were used; optimum loading was 1.58 wt.% Ru.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	as-prepared TMOF-10-NH2(I)	60 mg	10 · Synthesis of Ru@TMOF-10-NH2(I)
Metal Source	Ru NPs solution	0.2-1 mL · Ru:DMF = 2.0, 4.8, and 9.1 v/v%	10 · Synthesis of Ru@TMOF-10-NH2(I)
Solvent	DMF	10 mL	10 · Synthesis of Ru@TMOF-10-NH2(I)
Solvent	EtOH	wash three times	10 · Synthesis of Ru@TMOF-10-NH2(I)

Complete recipeSource: Both

Route 4: Solvothermal

10 · Synthesis of TMOF-10-NH2(Br)

Metal precursorsPbBr2 replacing PbI2 at the same molar ratio

Linker precursors2-aminoterephthalic acid at same molar ratio as TMOF-10-NH2(I)

SolventsDMF/EtOH mixed solvent, same recipe as TMOF-10-NH2(I)

Additivesperchloric acid, same recipe as TMOF-10-NH2(I)

Atmospheresealed Teflon-lined autoclave in stainless-steel vessel; atmosphere not otherwise specified

Temperature150

Time72

Work-upCool to room temperature; isolate crystals by vacuum filtration and rinse with EtOH.

ActivationFor sorption, incubate in EtOH at elevated temperature and vacuum dry at 80 °C overnight; outgas at 80 °C under <5 mm Hg for 600 min before gas sorption.

Scalability contextYield 0.175 g, 78% based on total Pb.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	PbBr2	same molar ratio as 0.5 mmol PbI2 recipe	10 · Synthesis of TMOF-10-NH2(Br)
Linker	2-aminoterephthalic acid	same as TMOF-10-NH2(I) route	10 · Synthesis of TMOF-10-NH2(Br)
Acid	perchloric acid (HClO4)	same as TMOF-10-NH2(I) route	10 · Synthesis of TMOF-10-NH2(Br)
Solvent	DMF/EtOH	4 mL in iodide route; same recipe · VDMF:VEtOH = 2:1	10 · Synthesis of TMOF-10-NH2(Br)

Complete recipeSource: Both

Route 5: Solvothermal

10 · Synthesis of TMOF-10-NH2(I)

Metal precursorsPbI2, 0.2305 g (0.5 mmol)

Linker precursors2-aminoterephthalic acid, 0.2715 g (1.50 mmol)

Solvents4 mL mixed DMF/EtOH, VDMF:VEtOH = 2:1

Additives200 uL perchloric acid (HClO4, 2.42 mmol); stoichiometric deionised water from acid source/added water noted as essential

Atmospheresealed Teflon-lined autoclave in stainless-steel vessel; atmosphere not otherwise specified

Temperature150

Time72

Work-upCool to room temperature; isolate brownish plate-like crystals by vacuum filtration; rinse with EtOH; manual grinding for micrometre powders.

ActivationFor sorption, incubate in EtOH at elevated temperature and vacuum dry at 80 °C overnight; outgas at 80 °C under <5 mm Hg for 600 min before gas sorption.

Scalability contextMain text reports high yield around 80% and gram-scale synthesis; detailed example yield 0.182 g, 77% based on total Pb.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	PbI2	0.2305 g; 0.5 mmol	10 · Synthesis of TMOF-10-NH2(I)
Linker	2-aminoterephthalic acid	0.2715 g; 1.50 mmol	10 · Synthesis of TMOF-10-NH2(I)
Acid	perchloric acid (HClO4, 70% in H2O)	200 uL; 2.42 mmol	10 · Synthesis of TMOF-10-NH2(I)
Solvent	N,N'-dimethylformamide	part of 4 mL mixed solvent · VDMF:VEtOH = 2:1	10 · Synthesis of TMOF-10-NH2(I)
Solvent	ethanol	part of 4 mL mixed solvent; rinse solvent · VDMF:VEtOH = 2:1	10 · Synthesis of TMOF-10-NH2(I)