Synthesis · A stable lanthanum hydroxamate metal-organic framework with radical character and electrical conductivity

6 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Solvothermal

5 · Experimental - Synthesis of Sm-ONDI · Fig. S23

Metal precursorsDy(NO3)3.6H2O

Linker precursorsH2ONDI, implied from analogous lanthanide ONDI synthesis

Solventsnot separately detailed; implied analogous to Sm/La ONDI synthesis

Additivesnot separately detailed

Atmospheresealed Teflon-lined autoclave implied

Temperaturenot separately detailed

Timenot separately detailed

Work-upmicrocrystalline material obtained

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Metal Source	Dy(NO3)3.6H2O	Not specified	5 · Experimental - Synthesis of Sm-ONDI · Fig. S23

Partial recipeSource: Main

Route 2: Solvothermal

5 · Experimental - Synthesis of Sm-ONDI · Fig. S23

Metal precursorsGd(NO3)3.6H2O

Linker precursorsH2ONDI, implied from analogous lanthanide ONDI synthesis

Solventsnot separately detailed; implied analogous to Sm/La ONDI synthesis

Additivesnot separately detailed

Atmospheresealed Teflon-lined autoclave implied

Temperaturenot separately detailed

Timenot separately detailed

Work-upmicrocrystalline material obtained

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Metal Source	Gd(NO3)3.6H2O	Not specified	5 · Experimental - Synthesis of Sm-ONDI · Fig. S23

Complete recipeSource: Both

Route 3: Solvothermal

4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S15

Metal precursorslanthanide chloride hydrate, same as La-ONDI-DMF route

Linker precursorsH2ONDI, same as La-ONDI-DMF route

SolventsDMF and HCl solution as in La-ONDI-DMF route

Additivescatechol, 5.5 mg, 0.05 mmol

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperaturesame procedure as La-ONDI-DMF/La-ONDI-DMA

Timesame procedure as La-ONDI-DMF/La-ONDI-DMA

Oxidant / reductantcatechol used to create a reducing environment and promote formation of NDI radical anion

Work-upsame procedure as La-ONDI-DMF; detailed isolated yield not reported separately

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	lanthanide chloride hydrates	same as La-ONDI-DMF route	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S15
Linker	H2ONDI	same as La-ONDI-DMF route	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S15
Solvent	DMF	same as La-ONDI-DMF route	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S15
Reductant	catechol	5.5 mg, 0.05 mmol	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S15
Acid	HCl	same as La-ONDI-DMF route · 1 M	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S15

Complete recipeSource: Both

Route 4: Solvothermal

5-6 · Experimental - Synthesis of La-ONDI; Gas adsorption experiments

Metal precursorslanthanide chloride hydrate, for La-ONDI interpreted as LaCl3 hydrate, 12 mg, about 0.05 mmol

Linker precursorsH2ONDI, 15 mg, 0.05 mmol

Solvents3 mL DMA; 1 mL 1 M HCl aqueous acid

Additives1 M HCl as acid modulator

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperatureheated from room temperature to 90 C in 7 h; held at 90 C

Time24 h hold at 90 C; cooled to 30 C in 15 h

Oxidant / reductantDMA solvent; dimethylamine from solvent decomposition discussed as reducing source for NDI ligand

Work-updeep brown crystals isolated by filtration and dried in air

ActivationFor gas adsorption activation: exchanged with fresh MeOH six times within 2 days, evacuated at 80 C and 5 x 10^-3 mbar overnight; for N2/CO2 adsorption, MeOH-exchanged La-ONDI degassed at 120 C using a turbomolecular pump for 12 h.

Scalability context18 mg product, 60% yield; sealed autoclave batch synthesis.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	lanthanide chloride hydrates	12 mg, about 0.05 mmol	5-6 · Experimental - Synthesis of La-ONDI; Gas adsorption experiments
Linker	H2ONDI	15 mg, 0.05 mmol	5-6 · Experimental - Synthesis of La-ONDI; Gas adsorption experiments
Solvent	DMA	3 mL	5-6 · Experimental - Synthesis of La-ONDI; Gas adsorption experiments
Acid	HCl	1 mL · 1 M	5-6 · Experimental - Synthesis of La-ONDI; Gas adsorption experiments

Complete recipeSource: Main

Route 5: Solvothermal

4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S22

Metal precursorslanthanide chloride hydrate, same as La-ONDI-DMA route

Linker precursorsH2ONDI, same as La-ONDI-DMA route

SolventsDMF replacing DMA; HCl solution as in La-ONDI-DMA route

Additives18-crown-6, 13 mg, 0.05 mmol

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperaturesame procedure as La-ONDI-DMA: ramp to 90 C in 7 h and hold at 90 C

Timesame procedure as La-ONDI-DMA: 24 h hold; cooled to 30 C in 15 h

Oxidant / reductantDMF solvent; faster decomposition to dimethylamine was proposed to increase NDI ligand reduction.

Work-upsame procedure as La-ONDI-DMA; detailed isolated yield not reported separately

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	lanthanide chloride hydrates	same as La-ONDI-DMA route	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S22
Linker	H2ONDI	same as La-ONDI-DMA route	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S22
Solvent	DMF	same solvent volume as DMA route, implied 3 mL	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S22
Additive	18-crown-6	13 mg, 0.05 mmol	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S22
Acid	HCl	same as La-ONDI-DMA route · 1 M	4-5 · Results and discussion; Experimental - Synthesis of La-ONDI · Fig. S22

Complete recipeSource: Main

Route 6: Solvothermal

5 · Experimental - Synthesis of Sm-ONDI

Metal precursorsSm(NO3)3, 10 mg, 0.05 mmol

Linker precursorsH2ONDI, 15 mg, 0.05 mmol

Solvents4 mL DMF and 2 mL 4 M HCl

Additives18-crown-6, 13 mg, 0.05 mmol

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperatureheated from room temperature to 90 C in 7 h; held at 90 C

Time48 h hold; cooled to 30 C in 15 h

Oxidant / reductantDMF solvent; no separate reductant reported

Work-upBrown crystals obtained together with light yellow microcrystalline by-product; work-up details beyond isolation not specified.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Sm(NO3)3	10 mg, 0.05 mmol	5 · Experimental - Synthesis of Sm-ONDI
Linker	H2ONDI	15 mg, 0.05 mmol	5 · Experimental - Synthesis of Sm-ONDI
Additive	18-crown-6	13 mg, 0.05 mmol	5 · Experimental - Synthesis of Sm-ONDI
Solvent	DMF	4 mL	5 · Experimental - Synthesis of Sm-ONDI
Acid	HCl	2 mL · 4 M	5 · Experimental - Synthesis of Sm-ONDI