Synthesis · From insulator to semiconductor: effect of host-guest interactions on charge transport in M-MOF-74 metal-organic frameworks

14 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

S-2 · Syntheses

Metal precursorsCopper nitrate trihydrate (1.18 g, 24.6 mmol)

Linker precursors2,5-dihydroxyterephthalic acid (dhtp) (0.44 g, 11.2 mmol)

Solvents20:1 (v/v) N,N-dimethylformamide (DMF)/2-propanol in a 100 mL screw-cap jar

AtmosphereCapped screw-cap jar; later dried with nitrogen gas

Temperature80

Time18

Work-upCooled to room temperature; mother liquor decanted; washed with 30 mL DMF once then 30 mL methanol four times over 48 h

ActivationVacuum at 150 deg C for 6 h

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Copper nitrate trihydrate	1.18 g, 24.6 mmol	S-2 · Syntheses
Linker	2,5-dihydroxyterephthalic acid (dhtp)	0.44 g, 11.2 mmol	S-2 · Syntheses
Solvent	N,N-dimethylformamide (DMF)	20:1 v/v with 2-propanol	S-2 · Syntheses
Solvent	2-propanol	20:1 v/v DMF/2-propanol	S-2 · Syntheses

Complete recipeSource: SI

Route 2: Other

S-4 · H4TCNQ Infiltration

Metal precursorsPreformed Cu-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM H4TCNQ

AtmosphereGlovebox; dry toluene

Temperatureroom temperature

Timeminimum 18

Oxidant / reductantH4TCNQ, recrystallised from hot methanol and dried

Work-upMother liquor exchanged several times with fresh toluene; powders dried under nitrogen gas

Activation120 deg C for 6 h under vacuum; stored in dry box

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed Cu-MOF-74 host	not reported	S-4 · H4TCNQ Infiltration
Other	(cyclohexane-1,4-diylidene)dimalononitrile (H4TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 · H4TCNQ Infiltration
Solvent	dry toluene	20 mL plus exchange solvent	S-4 · H4TCNQ Infiltration
Solvent	hot methanol for H4TCNQ recrystallisation	not reported	S-4 · H4TCNQ Infiltration

Partial recipeSource: SI

Route 3: Other

S-4 and S-9 · H4TCNQ Infiltration · Fig. S6

Metal precursorsPreformed Mg-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM H4TCNQ

AtmosphereGlovebox; dry toluene

Temperatureroom temperature

Timeminimum 18

Oxidant / reductantH4TCNQ, recrystallised from hot methanol and dried

Work-upMother liquor exchanged several times with fresh toluene; powders dried under nitrogen gas

Activation120 deg C for 6 h under vacuum; stored in dry box

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed Mg-MOF-74 host	not reported	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6
Other	(cyclohexane-1,4-diylidene)dimalononitrile (H4TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6
Solvent	dry toluene	20 mL plus exchange solvent	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6
Solvent	hot methanol for H4TCNQ recrystallisation	not reported	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6

Complete recipeSource: SI

Route 4: Other

S-4 · H4TCNQ Infiltration

Metal precursorsPreformed Mn-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM H4TCNQ

AtmosphereGlovebox; dry toluene

Temperatureroom temperature

Timeminimum 18

Oxidant / reductantH4TCNQ, recrystallised from hot methanol and dried

Work-upMother liquor exchanged several times with fresh toluene; powders dried under nitrogen gas

Activation120 deg C for 6 h under vacuum; stored in dry box

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed Mn-MOF-74 host	not reported	S-4 · H4TCNQ Infiltration
Other	(cyclohexane-1,4-diylidene)dimalononitrile (H4TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 · H4TCNQ Infiltration
Solvent	dry toluene	20 mL plus exchange solvent	S-4 · H4TCNQ Infiltration
Solvent	hot methanol for H4TCNQ recrystallisation	not reported	S-4 · H4TCNQ Infiltration

Partial recipeSource: SI

Route 5: Other

S-4 and S-9 · H4TCNQ Infiltration · Fig. S6

Metal precursorsPreformed Zn-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM H4TCNQ

AtmosphereGlovebox; dry toluene

Temperatureroom temperature

Timeminimum 18

Oxidant / reductantH4TCNQ, recrystallised from hot methanol and dried

Work-upMother liquor exchanged several times with fresh toluene; powders dried under nitrogen gas

Activation120 deg C for 6 h under vacuum; stored in dry box

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed Zn-MOF-74 host	not reported	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6
Other	(cyclohexane-1,4-diylidene)dimalononitrile (H4TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6
Solvent	dry toluene	20 mL plus exchange solvent	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6
Solvent	hot methanol for H4TCNQ recrystallisation	not reported	S-4 and S-9 · H4TCNQ Infiltration · Fig. S6

Partial recipeSource: SI

Route 6: Solvothermal

S-3 · Syntheses

Metal precursorsMagnesium nitrate hexahydrate (0.476 g, 1.11 mmol)

Linker precursorsdhtp (0.111 g, 0.56 mmol)

Solvents15:1:1 (v/v/v) DMF/ethanol/water in a 100 mL screw-cap jar; absolute solvent volumes not reported

AtmosphereCapped screw-cap jar; dried with nitrogen gas in vacuum

Temperature125

Time24

Work-upCooled to room temperature; mother liquor decanted; washed with 30 mL DMF once then 30 mL methanol three times; last methanol wash left overnight

ActivationActivation at 150 deg C for 6 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Magnesium nitrate hexahydrate	0.476 g, 1.11 mmol	S-3 · Syntheses
Linker	dhtp	0.111 g, 0.56 mmol	S-3 · Syntheses
Solvent	DMF/ethanol/water	not reported · 15:1:1 v/v/v	S-3 · Syntheses

Complete recipeSource: SI

Route 7: Solvothermal

S-2 · Syntheses

Metal precursorsManganese(II) chloride tetrahydrate (0.8784 g, 4.44 mmol)

Linker precursorsdhtp (0.2664 g, 1.345 mmol)

Solvents15:1:1 (v/v/v) DMF/ethanol/water (120 mL:8 mL:8 mL) in a 250 mL screw-cap jar

AtmosphereCapped screw-cap jar; dried with nitrogen gas

Temperature135

Time24

Work-upCooled to room temperature; mother liquor decanted; washed with 30 mL methanol six times over 72 h

ActivationDynamic vacuum at 150 deg C for 6 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Manganese(II) chloride tetrahydrate	0.8784 g, 4.44 mmol	S-2 · Syntheses
Linker	dhtp	0.2664 g, 1.345 mmol	S-2 · Syntheses
Solvent	DMF	120 mL · 15:1:1 v/v/v DMF/ethanol/water	S-2 · Syntheses
Solvent	ethanol	8 mL · 15:1:1 v/v/v	S-2 · Syntheses
Solvent	water	8 mL · 15:1:1 v/v/v	S-2 · Syntheses

Complete recipeSource: SI

Route 8: Other

S-3 · Syntheses

Metal precursorsManganese(II) nitrate tetrahydrate (0.1305 g, 0.5199 mmol)

Linker precursorsdhtp (0.0401 g, 0.2024 mmol)

Solvents7 mL DMF for synthesis; final DMSO/ethanol/ethylene glycol mixture 4:9:6 (v/v/v)

AdditivesTEA (0.17 mL)

AtmosphereRoom-temperature sonication; no inert atmosphere specified

Temperatureroom temperature

Time2

Substrate orientationPrinted onto FTO-coated glass

Work-upCentrifuged at 3000 rpm for 5 min; mother liquor replaced with fresh DMF and sonicated; centrifugation/DMF process repeated; final sample placed in DMSO/ethanol/ethylene glycol

ActivationNo thermal activation reported

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Manganese(II) nitrate tetrahydrate	0.1305 g, 0.5199 mmol	S-3 · Syntheses
Linker	dhtp	0.0401 g, 0.2024 mmol	S-3 · Syntheses
Base	TEA	0.17 mL	S-3 · Syntheses
Solvent	DMF	7 mL plus fresh wash DMF	S-3 · Syntheses
Solvent	DMSO/ethanol/ethylene glycol	4:9:6 v/v/v final mixture	S-3 · Syntheses
Other	FTO slide	one slide substrate	S-3 · Syntheses

Complete recipeSource: SI

Route 9: Other

S-4 · Guest Molecule Infiltration

Metal precursorsPreformed Mn-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM TCNQ

AtmosphereN2-filled MBraun 130-BG glovebox; toluene dried by alumina/molecular sieves

Temperatureroom temperature

Time12-48

Oxidant / reductantTCNQ conjugated acceptor guest; recrystallised from hot methanol and dried under vacuum

Work-upMother liquor exchanged 5 times with fresh toluene or until clear; powders dried under nitrogen gas

Activation150 deg C for 6-12 h; stored in dry box before conductivity measurements

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed M-MOF-74 host	not reported	S-4 · Guest Molecule Infiltration
Other	7,7,8,8-tetracyanoquinodimethane (TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 · Guest Molecule Infiltration
Solvent	dry toluene	20 mL plus wash/exchange solvent	S-4 · Guest Molecule Infiltration
Solvent	hot methanol for TCNQ recrystallisation	not reported	S-4 · Guest Molecule Infiltration

Complete recipeSource: SI

Route 10: Other

S-4 · Guest Molecule Infiltration

Metal precursorsPreformed Cu-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM TCNQ

AtmosphereN2-filled MBraun 130-BG glovebox; toluene dried by alumina/molecular sieves

Temperatureroom temperature

Time12-48

Oxidant / reductantTCNQ conjugated acceptor guest; recrystallised from hot methanol and dried under vacuum

Work-upMother liquor exchanged 5 times with fresh toluene or until clear; powders dried under nitrogen gas

Activation150 deg C for 6-12 h; stored in dry box before conductivity measurements

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed M-MOF-74 host	not reported	S-4 · Guest Molecule Infiltration
Other	7,7,8,8-tetracyanoquinodimethane (TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 · Guest Molecule Infiltration
Solvent	dry toluene	20 mL plus wash/exchange solvent	S-4 · Guest Molecule Infiltration
Solvent	hot methanol for TCNQ recrystallisation	not reported	S-4 · Guest Molecule Infiltration

Complete recipeSource: SI

Route 11: Other

S-4 · Guest Molecule Infiltration

Metal precursorsPreformed Mg-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM TCNQ

AtmosphereN2-filled MBraun 130-BG glovebox; toluene dried by alumina/molecular sieves

Temperatureroom temperature

Time12-48

Oxidant / reductantTCNQ conjugated acceptor guest; recrystallised from hot methanol and dried under vacuum

Work-upMother liquor exchanged 5 times with fresh toluene or until clear; powders dried under nitrogen gas

Activation150 deg C for 6-12 h; stored in dry box before conductivity measurements

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed M-MOF-74 host	not reported	S-4 · Guest Molecule Infiltration
Other	7,7,8,8-tetracyanoquinodimethane (TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 · Guest Molecule Infiltration
Solvent	dry toluene	20 mL plus wash/exchange solvent	S-4 · Guest Molecule Infiltration
Solvent	hot methanol for TCNQ recrystallisation	not reported	S-4 · Guest Molecule Infiltration

Complete recipeSource: SI

Route 12: Other

S-4 · Guest Molecule Infiltration

Metal precursorsPreformed Mn-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM TCNQ

AtmosphereN2-filled MBraun 130-BG glovebox; toluene dried by alumina/molecular sieves

Temperatureroom temperature

Time12-48

Oxidant / reductantTCNQ conjugated acceptor guest; recrystallised from hot methanol and dried under vacuum

Work-upMother liquor exchanged 5 times with fresh toluene or until clear; powders dried under nitrogen gas

Activation150 deg C for 6-12 h; stored in dry box before conductivity measurements

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed M-MOF-74 host	not reported	S-4 · Guest Molecule Infiltration
Other	7,7,8,8-tetracyanoquinodimethane (TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 · Guest Molecule Infiltration
Solvent	dry toluene	20 mL plus wash/exchange solvent	S-4 · Guest Molecule Infiltration
Solvent	hot methanol for TCNQ recrystallisation	not reported	S-4 · Guest Molecule Infiltration

Complete recipeSource: SI

Route 13: Other

S-4 · Guest Molecule Infiltration

Metal precursorsPreformed Zn-MOF-74 host

Linker precursorsPreformed MOF-74 framework

Solvents20 mL dry toluene saturated with 5 mM TCNQ

AtmosphereN2-filled MBraun 130-BG glovebox; toluene dried by alumina/molecular sieves

Temperatureroom temperature

Time12-48

Oxidant / reductantTCNQ conjugated acceptor guest; recrystallised from hot methanol and dried under vacuum

Work-upMother liquor exchanged 5 times with fresh toluene or until clear; powders dried under nitrogen gas

Activation150 deg C for 6-12 h; stored in dry box before conductivity measurements

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed M-MOF-74 host	not reported	S-4 · Guest Molecule Infiltration
Other	7,7,8,8-tetracyanoquinodimethane (TCNQ)	saturated solution in 20 mL toluene · 5 mM	S-4 · Guest Molecule Infiltration
Solvent	dry toluene	20 mL plus wash/exchange solvent	S-4 · Guest Molecule Infiltration
Solvent	hot methanol for TCNQ recrystallisation	not reported	S-4 · Guest Molecule Infiltration

Complete recipeSource: SI

Route 14: Solvothermal

S-2-S-3 · Syntheses

Metal precursorsZinc nitrate hexahydrate (1.021 g, 3.43 mmol)

Linker precursorsdhtp (0.250 g, 1.30 mmol)

Solvents50 mL DMF and 3 mL water in a 100 mL screw-cap jar

AtmosphereCapped screw-cap jar; dried with nitrogen gas in vacuum

Temperature100

Time24

Work-upCooled to room temperature; mother liquor decanted; washed with 30 mL DMF three times then 30 mL methanol three times; last methanol wash left overnight

ActivationActivation at 150 deg C for 6 h

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zinc nitrate hexahydrate	1.021 g, 3.43 mmol	S-2-S-3 · Syntheses
Linker	dhtp	0.250 g, 1.30 mmol	S-2-S-3 · Syntheses
Solvent	DMF	50 mL	S-2-S-3 · Syntheses
Solvent	water	3 mL	S-2-S-3 · Syntheses