Synthesis · High electrical conductivity and high porosity in a Guest@MOF material: Evidence of TCNQ ordering within Cu3BTC2 micropores

5 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Other

7410 · Experimental - Vapor phase infiltration

Metal precursorsCu3BTC2 product from literature synthesis; specific metal source not reported in this paper

Linker precursorsBTC in Cu3BTC2; specific linker amount not reported in this paper

Solventsethanol; dichloromethane

Atmospherehigh vacuum for desolvation

Temperature180

Timeone week ethanol Soxhlet and one week dichloromethane Soxhlet; desolvation time not stated

Work-upContinuous Soxhlet washing with ethanol and dichloromethane for one week each; each washing solvent replaced once with fresh solvent.

ActivationDesolvated under high vacuum (~10^-6 mbar) at 180 C.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Solvent	ethanol	Soxhlet for one week	7410 · Experimental - Vapor phase infiltration
Solvent	dichloromethane	Soxhlet for one week	7410 · Experimental - Vapor phase infiltration

Vague recipeSource: SI

Route 2: Other

S2, S10 · Powder X-ray diffraction / SEM images · Figures S1, S14

Metal precursorsnot specified; literature procedure

Linker precursorsTCNQ

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	Cu(TCNQ) literature procedure reagents	Not specified	S2, S10 · Powder X-ray diffraction / SEM images · Figures S1, S14

Complete recipeSource: SI

Route 3: Other

S15 · Liquid phase infiltration

Metal precursorspristine, activated Cu3BTC2

Linker precursorsTCNQ guest; BTC already in Cu3BTC2

Solventsdichloromethane (DCM)

Atmosphereambient drying; no inert condition stated for liquid infiltration

Temperatureroom temperature

Time120

Oxidant / reductantTCNQ redox-active guest; no added oxidant/reductant

Work-upGreen powder collected by filtration and dried in ambient air.

ActivationPristine activated Cu3BTC2 used.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	pristine, activated Cu3BTC2	150 mg	S15 · Liquid phase infiltration
Other	TCNQ	saturated solution · saturated in DCM	S15 · Liquid phase infiltration
Solvent	DCM	100 mL	S15 · Liquid phase infiltration

Partial recipeSource: SI

Route 4: Other

S2, S10-S11 · Powder X-ray diffraction / SEM images · Figures S2, S15-S17

Metal precursorsactivated, desolvated Cu3BTC2

Linker precursorsTCNQ guest

Solventsnone during VPI

Atmospheresealed vacuum ampoules; high-vacuum flame-sealed ampoules at 10^-5 mbar for 70 C sample

Temperature70-100

Oxidant / reductantTCNQ redox-active guest; no added oxidant/reductant

ActivationActivated/desolvated Cu3BTC2 used.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3BTC2	Not specified	S2, S10-S11 · Powder X-ray diffraction / SEM images · Figures S2, S15-S17
Other	TCNQ	0.5 or 1.0 equivalents in shown variants	S2, S10-S11 · Powder X-ray diffraction / SEM images · Figures S2, S15-S17

Complete recipeSource: Both

Route 5: Other

7406, 7410 · Results and Experimental - Vapor phase infiltration

Metal precursorsactivated, desolvated Cu3BTC2

Linker precursorsTCNQ guest; BTC already in Cu3BTC2

Solventsnone during VPI; TCNQ recrystallised from acetonitrile before use

Atmosphereargon glovebox; sealed evacuated borosilicate glass tube (~10^-3 mbar)

Temperature180

Time72

Oxidant / reductantTCNQ redox-active guest; no added oxidant/reductant

Work-upAmpoules cooled to room temperature, transferred into glovebox and stored for characterisation; no washing step.

ActivationCu3BTC2 pre-desolvated under high vacuum at 180 C; TCNQ recrystallised three times from acetonitrile under inert conditions.

Scalability contextBatch used 200 mg Cu3BTC2 with distinct TCNQ amounts for concentration series.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3BTC2	200 mg	7406, 7410 · Results and Experimental - Vapor phase infiltration
Other	TCNQ	distinct amounts to prepare x = 0.1, 0.2, ..., 1.0	7406, 7410 · Results and Experimental - Vapor phase infiltration
Solvent	acetonitrile	used for three recrystallisations of TCNQ	7406, 7410 · Results and Experimental - Vapor phase infiltration