Synthesis · An Electrically Conducting Li-Ion Metal-Organic Framework

10 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

4 · 1.2.5 · Figure S5

Metal precursorsH2-Mg-DOBDC.DMF2

Atmospherevacuum oven inside glovebox

Temperature200

Time32

Activationheated in a vacuum oven inside glovebox at 200 degC for 32 h

Scalability context100 mg scale for desolvation.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	solvated H2-Mg-DOBDC	100 mg scale	4 · 1.2.5 · Figure S5

Complete recipeSource: SI

Route 2: Solvothermal

4 · 1.2.3

Metal precursorsMg(NO3)2.6H2O (0.256 g, 1 mmol)

Linker precursors2,5-dihydroxyterephthalic acid (0.200 g, 1 mmol)

SolventsDMF (16 mL)

Additivestriethylamine (30 microL)

Atmospheresealed Teflon reactor in stainless-steel autoclave

Temperature120

Time72

Work-upcooled to ambient temperature; product isolated by filtration and washed with DMF

Scalability context1 mmol solvothermal route; yield 57%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Mg(NO3)2.6H2O	0.256 g, 1 mmol	4 · 1.2.3
Linker	2,5-dihydroxyterephthalic acid	0.200 g, 1 mmol	4 · 1.2.3
Solvent	DMF	16 mL	4 · 1.2.3
Base	triethylamine	30 microL	4 · 1.2.3

Complete recipeSource: Both

Route 3: Other

4 · 1.2.5 · Figure S2

Metal precursorsH2-Mn-DOBDC.DMF2

Atmospherevacuum oven inside glovebox

Temperature200

Time32

Activationheated in a vacuum oven inside glovebox at 200 degC for 32 h

Scalability context100 mg scale for desolvation.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	solvated H2-Mn-DOBDC	100 mg scale	4 · 1.2.5 · Figure S2

Complete recipeSource: SI

Route 4: Other

3 · 1.2.2

Metal precursorsMn(NO3)2.4H2O (2.5 g, 10 mmol)

Linker precursors2,5-dihydroxyterephthalic acid (2 g, 10 mmol)

SolventsDMF (160 mL)

Additivestriethylamine (2 mL) added dropwise

Atmospherenot specified

Temperatureroom temperature; vacuum dry at 60 degC

Time0.5 reaction; 12 drying

Work-upvacuum filtration; washed with DMF (3 x 50 mL)

Activationvacuum dried at 60 degC for 12 h

Scalability context10 mmol bulk crystalline powder synthesis; yield 69%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Mn(NO3)2.4H2O	2.5 g, 10 mmol	3 · 1.2.2
Linker	2,5-dihydroxyterephthalic acid	2 g, 10 mmol	3 · 1.2.2
Solvent	DMF	160 mL	3 · 1.2.2
Base	triethylamine	2 mL	3 · 1.2.2

Complete recipeSource: SI

Route 5: Liquid Liquid Interface

3 · 1.2.1

Metal precursorsMn(NO3)2.4H2O (63 mg, 0.25 mmol)

Linker precursors2,5-dihydroxyterephthalic acid (50 mg, 0.25 mmol)

SolventsDMF (2.5 mL in vial; 3 mL in outer container)

Additivestriethylamine (50 microL) in outer DMF container

Atmospheresealed glass container; atmosphere not otherwise specified

Temperatureroom temperature

Time96

Work-uppale yellow crystals obtained after four days

Scalability contextDiffusion single-crystal route; bulk powder route used for further study.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Mn(NO3)2.4H2O	63 mg, 0.25 mmol	3 · 1.2.1
Linker	2,5-dihydroxyterephthalic acid	50 mg, 0.25 mmol	3 · 1.2.1
Solvent	DMF	2.5 mL + 3 mL	3 · 1.2.1
Base	triethylamine	50 microL	3 · 1.2.1

Partial recipeSource: SI

Route 6: Other

6 · 1.2.11 · Figure S8

Metal precursorsLi2-Mn-DOBDC

SolventsTHF, as for Li1.5-Mn-DOBDC

Atmosphereinside glovebox

Temperatureroom temperature reaction; drying as similar procedure

Timesimilar procedure to Li1.5-Mn-DOBDC

Oxidant / reductantdichloro-5,6-dicyano-1,4-benzoquinone doubled to 0.2 mmol

Work-upsimilar procedure to Li1.5-Mn-DOBDC

Activationsimilar procedure to Li1.5-Mn-DOBDC

Scalability contextYield 91%; exact repeated solvent/workup quantities omitted by source.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Li2-Mn-DOBDC	not restated	6 · 1.2.11 · Figure S8
Oxidant	DCBQ	0.2 mmol	6 · 1.2.11 · Figure S8
Solvent	THF	not restated; similar to Li1.5-Mn-DOBDC	6 · 1.2.11 · Figure S8

Complete recipeSource: SI

Route 7: Other

5 · 1.2.10 · Figure S8

Metal precursorsLi2-Mn-DOBDC (105 mg, 0.4 mmol)

SolventsTHF (3 mL) plus DCBQ solution in THF (3 mL)

Atmosphereinside glovebox

Temperatureroom temperature reaction; 70 degC drying

Time72 reaction; 3 drying

Oxidant / reductantdichloro-5,6-dicyano-1,4-benzoquinone (DCBQ; 3 mL, 0.1 mmol in THF)

Work-upcentrifugation; washed with THF (3 x 6 mL)

Activationvacuum dried at 70 degC for 3 h

Scalability contextYield 87%.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Li2-Mn-DOBDC	105 mg, 0.4 mmol	5 · 1.2.10 · Figure S8
Solvent	THF	3 mL + 3 mL	5 · 1.2.10 · Figure S8
Oxidant	dichloro-5,6-dicyano-1,4-benzoquinone	3 mL, 0.1 mmol · anhydrous solution in THF	5 · 1.2.10 · Figure S8

Partial recipeSource: SI

Route 8: Other

5 · 1.2.7

Metal precursorsH2-Mg-DOBDC

Solventsanhydrous THF and anhydrous methanolic LiOCH3 solution, as for Li2-Mn-DOBDC

AdditivesLiOCH3, as for Li2-Mn-DOBDC

AtmosphereAr-filled glovebox

Temperatureroom temperature reaction; vacuum dry as Li2-Mn-DOBDC procedure

Timeas Li2-Mn-DOBDC procedure

Oxidant / reductantLiOCH3 used for H-Li exchange/deprotonation

Work-upsimilar to Li2-Mn-DOBDC procedure

Activationsimilar to Li2-Mn-DOBDC procedure

Scalability contextYield 86%; exact Mg precursor amount not restated, procedure described by analogy.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	H2-Mg-DOBDC	not restated	5 · 1.2.7
Base	LiOCH3	not restated; similar procedure to Li2-Mn-DOBDC · anhydrous methanolic solution	5 · 1.2.7
Solvent	anhydrous THF	not restated	5 · 1.2.7

Complete recipeSource: Both

Route 9: Other

4-5 · 1.2.6 · Figure 1

Metal precursorsH2-Mn-DOBDC (125 mg, 0.5 mmol)

Solventsanhydrous THF (5 mL); anhydrous methanolic LiOCH3 solution

AdditivesLiOCH3 (5.5 mL, 1.2 mmol)

AtmosphereAr-filled glovebox; anhydrous solvents, O2/H2O below 0.5 ppm

Temperatureroom temperature reaction; 180 degC vacuum dry

Time72 reaction; 5 drying

Oxidant / reductantLiOCH3 used for H-Li exchange/deprotonation

Work-upretrieved by centrifugation at 4000 rpm; washed with anhydrous THF (3 x 10 mL)

Activationvacuum dried at 180 degC for 5 h

Scalability context0.5 mmol H2-Mn-DOBDC scale; yield 81%.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	H2-Mn-DOBDC	125 mg, 0.5 mmol	4-5 · 1.2.6 · Figure 1
Solvent	anhydrous THF	5 mL	4-5 · 1.2.6 · Figure 1
Base	LiOCH3	5.5 mL, 1.2 mmol · anhydrous methanolic solution	4-5 · 1.2.6 · Figure 1

Complete recipeSource: SI

Route 10: Other

4 · 1.2.4

Metal precursorsMn(NO3)2.4H2O (3 mmol in 3 mL methanol)

Linker precursors2,5-dihydroxyterphthalic acid (198 mg, 1 mmol)

Solventsmethanol (8 mL + 3 mL metal solution + 3 mL additional)

AdditivesNaOH (160 mg, 4 mmol)

Atmosphereargon during initial stirring

Temperatureroom temperature reaction; 70 degC vacuum dry; 120 degC thermal treatment

Time24 reaction; overnight drying; 5 activation

Work-upfiltered; washed three times with methanol; vacuum dried at 70 degC overnight

Activationthermally treated at 120 degC for 5 h to remove guest solvent molecules

Scalability context1 mmol linker scale; yield 63%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,5-dihydroxyterphthalic acid	198 mg, 1 mmol	4 · 1.2.4
Base	NaOH	160 mg, 4 mmol	4 · 1.2.4
Metal Source	Mn(NO3)2.4H2O	3 mmol in 3 mL methanol	4 · 1.2.4
Solvent	methanol	8 mL + 3 mL + 3 mL	4 · 1.2.4