Synthesis · Conjugated crosslinks boost the conductivity and stability of a single crystalline metal-organic framework

9 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

SI p.S9-S10 · Synthesis of CH3BPD-4F4TS · Fig. S1

Linker precursors2,2',3,3',5,5',6,6'-octafluoro-[1,1'-biphenyl]-4,4'-dicarboxylate (OFBPD); 2-thiophenethiol

Solventsdry DMF; extraction with ethyl acetate; column eluent PE and EA

Additivespotassium carbonate

Atmosphereflask capped; atmosphere not otherwise specified

Temperatureroom temperature

Time2

Work-uppoured into water, extracted with ethyl acetate, washed with water, dried over anhydrous MgSO4, solvent removed, silica column chromatography; pink solid 2.7 g, 68% yield

Activationnot applicable

Scalability context100 mL flask, gram-scale precursor route.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,2',3,3',5,5',6,6'-octafluoro-[1,1'-biphenyl]-4,4'-dicarboxylate (OFBPD)	2.06 g, 4.97 mmol	SI p.S9-S10 · Synthesis of CH3BPD-4F4TS · Fig. S1
Base	potassium carbonate	3.74 g, 27.1 mmol	SI p.S9-S10 · Synthesis of CH3BPD-4F4TS · Fig. S1
Solvent	dry DMF	26 mL + 4 mL	SI p.S9-S10 · Synthesis of CH3BPD-4F4TS · Fig. S1
Linker	2-thiophenethiol	2 mL	SI p.S9-S10 · Synthesis of CH3BPD-4F4TS · Fig. S1
Solvent	ethyl acetate	3 x 30 mL extraction	SI p.S9-S10 · Synthesis of CH3BPD-4F4TS · Fig. S1

Complete recipeSource: SI

Route 2: Other

SI p.S10-S11 · Synthesis of H2BPD-4F4TS · Fig. S1

Linker precursorsCH3BPD-4F4TS

SolventsEtOH/H2O; water/HCl workup

AdditivesNaOH; HCl 10% for precipitation

AtmosphereN2 protection; flask evacuated/refilled with N2 three times; solution degassed and injected under N2

Temperaturereflux

Time3

Work-upcooled, poured into water and 10% HCl with vigorous stirring, pH kept below 2, suction filtration, washed with water, dried; 1.88 g, 95.4% yield

Activationdried for solvothermal synthesis without further purification

Scalability context100 mL flask, gram-scale linker hydrolysis route.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	CH3BPD-4F4TS	2.04 g, 2.56 mmol	SI p.S10-S11 · Synthesis of H2BPD-4F4TS · Fig. S1
Base	NaOH	2.4 g, 60 mmol	SI p.S10-S11 · Synthesis of H2BPD-4F4TS · Fig. S1
Solvent	EtOH	20 mL	SI p.S10-S11 · Synthesis of H2BPD-4F4TS · Fig. S1
Solvent	H2O	10 mL + 50 mL workup	SI p.S10-S11 · Synthesis of H2BPD-4F4TS · Fig. S1
Acid	HCl	used for precipitation · 10%	SI p.S10-S11 · Synthesis of H2BPD-4F4TS · Fig. S1

Complete recipeSource: SI

Route 3: Other

SI p.S13 · Solution polymerization · Fig. S38-S39

Linker precursorsH2BPD-4F4TS

Solventsanhydrous dichloromethane; washed with methanol, dichloromethane and acetone

AdditivesFeCl3

Atmospheresealed Schlenk tube with Teflon cap; atmosphere not further specified

Temperature60

Time2

Oxidant / reductantFeCl3 oxidant

Work-upcool to room temperature; insoluble yellow solid collected by suction filtration; washed with methanol (5 x 10 mL), dichloromethane (5 x 10 mL) and acetone (3 x 10 mL); dried in air; yield 39 mg, 78.4%

Activationnot applicable

Scalability context50 mg linker batch.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H2BPD-4F4TS	50 mg, 0.065 mmol	SI p.S13 · Solution polymerization · Fig. S38-S39
Oxidant	FeCl3	126 mg, 0.78 mmol	SI p.S13 · Solution polymerization · Fig. S38-S39
Solvent	anhydrous dichloromethane	5 mL	SI p.S13 · Solution polymerization · Fig. S38-S39

Complete recipeSource: SI

Route 4: Other

SI p.S14 · Preparation of H2SO4@ZrBPD-4F4TS-Ox · Fig. 3; Table S3

Metal precursorsas-made ZrBPD-4F4TS-Ox

Linker precursorscrosslinked BPD-4F4TS framework

Solvents1 M H2SO4 aqueous solution

AdditivesH2SO4

Atmosphereglass vial, room temperature; atmosphere not specified

Temperatureroom temperature; dried at 60

Time1 h acid stirring; 2 h drying

Work-upisolated by centrifugation and dried at 60 deg C for 2 h

Activationacid treatment of as-made ZrBPD-4F4TS-Ox

Scalability context15 mg sample batch.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	as-made ZrBPD-4F4TS-Ox	15 mg	SI p.S14 · Preparation of H2SO4@ZrBPD-4F4TS-Ox · Fig. 3; Table S3
Acid	H2SO4 aqueous solution	10 mL glass vial containing solution; volume not specified · 1 M	SI p.S14 · Preparation of H2SO4@ZrBPD-4F4TS-Ox · Fig. 3; Table S3

Complete recipeSource: SI

Route 5: Other

SI p.S12-S13 · Treatment by HF and HCl solution · Fig. S14-S19

Metal precursorsas-made ZrBPD-4F4TS or ZrBPD-4F4TS-Ox

Linker precursorsBPD-4F4TS framework

SolventsDMSO

Additiveshydrochloric acid; sodium fluoride generating HF

Atmosphereglass bottle; oil bath; atmosphere not specified

Temperature85

Time0.5

Work-upcentrifuged supernatants used for 1H and 19F NMR measurements

Activationnot applicable

Scalability context15 mg stability-test batch.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	as-made ZrBPD-4F4TS or ZrBPD-4F4TS-Ox	about 15 mg · about 2.1 mg, 0.023 mmol Zr	SI p.S12-S13 · Treatment by HF and HCl solution · Fig. S14-S19
Solvent	dimethyl sulfoxide	2 mL	SI p.S12-S13 · Treatment by HF and HCl solution · Fig. S14-S19
Acid	hydrochloric acid	40 uL or 120 uL · 36% by weight; 0.36% or 1.8% HCl by weight in solution	SI p.S12-S13 · Treatment by HF and HCl solution · Fig. S14-S19
Additive	sodium fluoride	10 mg · equivalent to 0.2% HF by weight	SI p.S12-S13 · Treatment by HF and HCl solution · Fig. S14-S19

Complete recipeSource: SI

Route 6: Other

SI p.S11-S12 · Activation of ZrBPD-4F4TS · Fig. S32-S37

Metal precursorsas-made ZrBPD-4F4TS crystals

Linker precursorsBPD-4F4TS framework

Solventsacetone

AtmosphereSoxhlet extraction under reflux; final vacuum heating

Temperature100 then 120

Time72 h Soxhlet; vacuum time not reported

Work-upfilter-paper thimble removed after Soxhlet extraction

ActivationSoxhlet extraction in acetone (150 mL) at 100 deg C for 3 days, then heat at 120 deg C under vacuum

Scalability context100 mg sample batch in Soxhlet extractor.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	as-made ZrBPD-4F4TS crystals	100 mg	SI p.S11-S12 · Activation of ZrBPD-4F4TS · Fig. S32-S37
Solvent	acetone	150 mL	SI p.S11-S12 · Activation of ZrBPD-4F4TS · Fig. S32-S37

Complete recipeSource: SI

Route 7: Other

SI p.S12 · Activation of ZrBPD-4F4TS-Ox · Fig. 2f

Metal precursorsas-made ZrBPD-4F4TS-Ox

Linker precursorscrosslinked BPD-4F4TS framework

Solventsmethanol

AtmosphereSoxhlet extraction under reflux; final vacuum heating

Temperature100 then 120

Time72 h Soxhlet; vacuum time not reported

Work-upfilter-paper thimble removed after Soxhlet extraction

ActivationSoxhlet extraction in methanol (150 mL) at 100 deg C for 3 days, then heat at 120 deg C under vacuum

Scalability context100 mg sample batch in Soxhlet extractor.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	as-made ZrBPD-4F4TS-Ox	100 mg	SI p.S12 · Activation of ZrBPD-4F4TS-Ox · Fig. 2f
Solvent	methanol	150 mL	SI p.S12 · Activation of ZrBPD-4F4TS-Ox · Fig. 2f

Complete recipeSource: SI

Route 8: Other

SI p.S12 · Preparation of ZrBPD-4F4TS-Ox · Fig. 1

Metal precursorsactivated ZrBPD-4F4TS

Linker precursorsBPD-4F4TS framework pendant thiophene groups

Solventsnitromethane; toluene

AdditivesFeCl3

Atmospheresealed 25 mL Schlenk tube with Teflon cap; atmosphere not further specified

Temperature90

Time120

Oxidant / reductantFeCl3 oxidant, 400 mg, 2.47 mmol; main text states 6:1 FeCl3/thiophene molar ratio used for thorough polymerisation

Work-upnatural cooling; brown powder washed several times with nitromethane, methanol and acetone; dried in air

Activationseparate methanol Soxhlet activation route reported for activated ZrBPD-4F4TS-Ox

Scalability context100 mg activated MOF batch.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated ZrBPD-4F4TS	100 mg, 0.026 mmol	SI p.S12 · Preparation of ZrBPD-4F4TS-Ox · Fig. 1
Oxidant	FeCl3	400 mg, 2.47 mmol · 6:1 FeCl3/thiophene molar ratio stated in main text	SI p.S12 · Preparation of ZrBPD-4F4TS-Ox · Fig. 1
Solvent	nitromethane	15 mL	SI p.S12 · Preparation of ZrBPD-4F4TS-Ox · Fig. 1
Solvent	toluene	5 mL	SI p.S12 · Preparation of ZrBPD-4F4TS-Ox · Fig. 1

Complete recipeSource: SI

Route 9: Solvothermal

SI p.S11 · Self-assembly synthesis of ZrBPD-4F4TS · Fig. S9

Metal precursorsZrCl4

Linker precursorsH2BPD-4F4TS

SolventsDMF

Additivestrifluoroacetic acid

Atmospheresealed 25 mL Schlenk tube with Teflon cap; atmosphere not further specified

Temperature120

Time72

Work-upnatural cooling; freshly prepared crystals immersed in DMF (4 mL) three times, soaked 6 h at 80 deg C each time before decanting; 144 mg, 15% yield based on H2BPD-4F4TS

Activationseparate Soxhlet activation route reported for activated sample

Scalability context25 mL Schlenk tube batch; 144 mg isolated yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	450 mg, 1.93 mmol	SI p.S11 · Self-assembly synthesis of ZrBPD-4F4TS · Fig. S9
Linker	H2BPD-4F4TS	720 mg, 0.94 mmol	SI p.S11 · Self-assembly synthesis of ZrBPD-4F4TS · Fig. S9
Acid	trifluoroacetic acid	276 mg, 2.42 mmol	SI p.S11 · Self-assembly synthesis of ZrBPD-4F4TS · Fig. S9
Solvent	DMF	18 mL + 4 mL washes	SI p.S11 · Self-assembly synthesis of ZrBPD-4F4TS · Fig. S9