Synthesis · Cation-exchanged conductive Mn2DSBDC metal–organic frameworks: Synthesis, structure, and THz conductivity

7 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

2 · 2.6 Cation exchange procedure

Metal precursorscobalt acetylacetonate, Co(acac)2

Linker precursorspre-formed Mn2DSBDC framework

Solventsdry DMF 30 mL; methanol rinse

Additivesnone

Atmosphereair-free; pressure tube evacuated and filled with nitrogen three times

Temperature100

Time21

Work-upRinsed three times with DMF and once with methanol via centrifugation; dried under ambient conditions.

Activationnot reported beyond ambient drying

Scalability contextExchange target approximately 10 at%; XRF found 10.2 at% Co with respect to Mn.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Mn2DSBDC	140 mg	2 · 2.6 Cation exchange procedure
Metal Source	Co(acac)2	47.2 mg; 0.0183 mmol	2 · 2.6 Cation exchange procedure
Solvent	dry DMF	30 mL	2 · 2.6 Cation exchange procedure

Complete recipeSource: Main

Route 2: Other

2 · 2.6 Cation exchange procedure · Fig. 2d

Metal precursorscopper acetylacetonate, Cu(acac)2

Linker precursorspre-formed Mn2DSBDC framework

Solventsdry DMF 30 mL inferred same procedure; methanol rinse

Additivesnone

Atmosphereair-free; same procedure as Co@Mn2DSBDC

Temperature100

Time21

Work-upSame rinsing/drying procedure as Co@Mn2DSBDC: DMF three times, methanol once by centrifugation, ambient drying.

Activationnot reported beyond ambient drying

Scalability contextApproximately 5x less Cu(acac)2 was required; XRF found 8.2 at% Cu with respect to Mn.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Mn2DSBDC	150 mg	2 · 2.6 Cation exchange procedure · Fig. 2d
Metal Source	Cu(acac)2	10.0 mg, 0.038 mmol	2 · 2.6 Cation exchange procedure · Fig. 2d
Solvent	dry DMF	30 mL, inferred same procedure	2 · 2.6 Cation exchange procedure · Fig. 2d

Complete recipeSource: Both

Route 3: Other

2 · 2.4 Synthesis of H2DSBDC · Fig. S1

Metal precursorsnone

Linker precursorsS3

Solventsethanol/water (1:1, v/v), 16 mL; 2 M HCl aq. 50 mL; water washes

Additivessodium hydroxide; hydrochloric acid

Atmospheredeaerated solution; reflux under N2

Temperaturereflux

Time3

Work-upCooled, poured into 2 M HCl (50 mL), filtered under reduced pressure, washed three times with water (70 mL), dried under high vacuum.

Activationnot applicable

Scalability contextReported isolated yield 340 mg, 85%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	S3	745 mg, 1.74 mmol, 1.0 equiv	2 · 2.4 Synthesis of H2DSBDC · Fig. S1
Base	sodium hydroxide	in 16 mL ethanol/water · 1.3 M	2 · 2.4 Synthesis of H2DSBDC · Fig. S1
Solvent	ethanol/water	16 mL · 1:1 v/v	2 · 2.4 Synthesis of H2DSBDC · Fig. S1
Acid	HCl aqueous	50 mL · 2 M	2 · 2.4 Synthesis of H2DSBDC · Fig. S1

Complete recipeSource: Both

Route 4: Solvothermal

2 · 2.5 Synthesis of Mn2DSBDC MOF · Fig. S2

Metal precursorsMnCl2·4H2O

Linker precursorsH2DSBDC

Solventsdry DMF 9.9 mL; methanol 4.8 mL

Additivesnone

Atmosphereair-free; three freeze-pump-thaw cycles; nitrogen refill

Temperature120

Timeabout 21

Work-upAir-stable yellow precipitate collected by vacuum filtration and washed with 10 mL methanol and 10 mL DMF; products pXRD checked before combining.

ActivationNo activation used for studied as-prepared material; text notes CH2Cl2 exchange/drying can remove solvent in activated form in prior work.

Scalability contextOne synthesis gave about 160.2 mg; procedure repeated four times to yield >600 mg undoped Mn2DSBDC.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	MnCl2·4H2O	377.2 mg, 1.91 mmol	2 · 2.5 Synthesis of Mn2DSBDC MOF · Fig. S2
Linker	H2DSBDC	83.1 mg, 0.36 mmol	2 · 2.5 Synthesis of Mn2DSBDC MOF · Fig. S2
Solvent	dry DMF	9.9 mL	2 · 2.5 Synthesis of Mn2DSBDC MOF · Fig. S2
Solvent	methanol	4.8 mL	2 · 2.5 Synthesis of Mn2DSBDC MOF · Fig. S2

Complete recipeSource: Main

Route 5: Other

2 · 2.6 Cation exchange procedure

Metal precursorsnickel acetylacetonate, Ni(acac)2

Linker precursorspre-formed Mn2DSBDC framework

Solventsdry DMF 30 mL inferred same procedure; methanol rinse

Additivesnone

Atmosphereair-free; same procedure as Co@Mn2DSBDC

Temperature100

Time21

Work-upSame rinsing/drying procedure as Co@Mn2DSBDC: DMF three times, methanol once by centrifugation, ambient drying.

Activationnot reported beyond ambient drying

Scalability contextXRF found 7.5 at% Ni with respect to Mn.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Mn2DSBDC	164 mg	2 · 2.6 Cation exchange procedure
Metal Source	Ni(acac)2	55.2 mg, 0.215 mmol	2 · 2.6 Cation exchange procedure
Solvent	dry DMF	30 mL, inferred same procedure	2 · 2.6 Cation exchange procedure

Complete recipeSource: Both

Route 6: Other

2 · 2.2 Synthesis of S2 · Fig. S1

Metal precursorsnone

Linker precursorsdiethyl 2,5-dihydroxyterephthalate (S1)

Solventsanhydrous N,N-dimethylacetamide (DMA), 10 mL + 2.5 mL

AdditivesDABCO base; dimethylthiocarbamoyl chloride

AtmosphereN2 purge

Temperature0 °C addition, then room temperature

Time17

Work-upDiluted with water (50 mL), filtered, washed with water (200 mL), dried under high vacuum.

Activationnot applicable

Scalability contextReported isolated yield 828 mg, 98%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	diethyl 2,5-dihydroxyterephthalate (S1)	500 mg, 1.97 mmol, 1.0 equiv	2 · 2.2 Synthesis of S2 · Fig. S1
Base	1,4-diazabicyclo[2.2.2]octane (DABCO)	884 mg, 7.88 mmol, 4.0 equiv	2 · 2.2 Synthesis of S2 · Fig. S1
Solvent	anhydrous N,N-dimethylacetamide (DMA)	10 mL + 2.5 mL	2 · 2.2 Synthesis of S2 · Fig. S1
Other	dimethylthiocarbamoyl chloride	974 mg, 7.88 mmol, 4.0 equiv	2 · 2.2 Synthesis of S2 · Fig. S1

Complete recipeSource: Both

Route 7: Other

2 · 2.3 Synthesis of S3 · Fig. S1

Metal precursorsnone

Linker precursorsS2

Solventsboiling ethanol workup, 20 mL

Additivesnone

AtmosphereN2 purge; balloon attached to balance pressure

Temperature215

Time1

Work-upAdded 20 mL boiling ethanol, cooled to room temperature, centrifuged at 3000 x g for 15 min, discarded supernatant, dried precipitate under high vacuum.

Activationnot applicable

Scalability contextReported isolated yield 745 mg, 74%.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	S2	1.00 g, 2.33 mmol	2 · 2.3 Synthesis of S3 · Fig. S1
Solvent	ethanol	20 mL, boiling	2 · 2.3 Synthesis of S3 · Fig. S1