Synthesis · Tunneling Electrical Connection to the Interior of Metal-Organic Frameworks

5 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Drop Cast

19 · Section 10 · Figure S12

Metal precursorspreformed AgNC@MIL-53; Au electrodes

Linker precursorspreformed AgNC@MIL-53

Solventsethanol suspension implied by Figure S12 label Ag@MIL in ethanol

Additives0.3 mm Cu wire spacer/mask removed after sputtering

Atmospherenot reported

Temperature150 C anneal

Timeanneal time not reported

Substrate orientationglass substrate; Au electrodes sputtered around Cu wire gap

Oxidant / reductantnone during film fabrication

Work-upspread/doctor blade film on glass; annealed to remove organic residues; sputter-deposited Au electrodes; removed Cu wire

Activationannealed at 150 C to remove organic residues

Scalability contextThin-film device fabrication schematic rather than full scalable process.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	AgNC@MIL-53 in ethanol	not reported	19 · Section 10 · Figure S12
Other	glass substrate	not reported	19 · Section 10 · Figure S12
Other	Au electrodes	not reported	19 · Section 10 · Figure S12
Other	Cu wire	0.3 mm	19 · Section 10 · Figure S12

Complete recipeSource: SI

Route 2: Other

2-3 · Section 1 · Experimental Methods

Metal precursorsMIL-53 MOF (Al), Basolite A100; Ag(I) nitrate 256 mg, 1.5 mmol

Linker precursorspreformed commercial MIL-53(Al)

Solvents500 uL nanopure water diluted to 3 mL with 200-proof ethanol; 5:1 ethanol/water AgNO3 solution

Additivesnone reported

Atmospherereaction vessel backfilled with N2; activation/reactivation under vacuum

Temperature180 C initial activation; room-temperature infiltration; 100 C reactivation

Time16 h initial activation; 2 min sonication; 16 h shaking at 250 rpm; 16 h reactivation

Substrate orientationnot applicable

Oxidant / reductantAgNO3; reducing chemistry follows Houk et al. procedure, not further specified here

Work-upwashed three times with ethanol to remove excess salt or unbound Ag particles

Activationactivated under 10^-1 Torr at 180 C for 16 h, evacuated at 10^-2 Torr; after washing reactivated at 100 C and 10^-1 Torr for 16 h

Scalability contextBatch using approximately 100 mg MIL-53 and 3 mL of 0.5 M AgNO3 solution.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MIL-53 MOF (Al) (Basolite A100, Sigma-Aldrich)	approximately 100 mg	2-3 · Section 1 · Experimental Methods
Metal Source	Ag(I) nitrate	256 mg, 1.5 mmol · 0.5 M after dilution	2-3 · Section 1 · Experimental Methods
Solvent	nanopure water	500 uL	2-3 · Section 1 · Experimental Methods
Solvent	200-proof ethanol	diluted to 3 mL total · 5:1 ethanol/water	2-3 · Section 1 · Experimental Methods

Complete recipeSource: Both

Route 3: Other

2 · Section 1 · Experimental Methods

Metal precursorsAgNO3 in acetonitrile, typically 10 mM; also 0.5, 1, 2, 5 mM variants

Linker precursorspreformed Rb-CD-MOF crystals

Solventsacetonitrile

Additivesnone reported

Atmospherenot specified during soaking; stored in acetonitrile; degassed under vacuum before measurements

Temperatureroom temperature/not specified

Time48 h AgNO3 immersion; washed over 48 h

Substrate orientationnot applicable

Oxidant / reductantAg+ reduced by hydroxide anions alone or cooperatively with cyclodextrins in Rb-CD-MOF

Work-upremoved from reaction solution, washed several times with acetonitrile over 48 h to remove salts, stored in acetonitrile

Activationdegassed under vacuum (<0.1 mTorr) in MMR chamber for 48 h prior to conductance measurements

Scalability contextTypically 30 single crystals per AgNO3 soaking batch.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	freshly synthesized Rb-CD-MOF crystals	30 pieces	2 · Section 1 · Experimental Methods
Metal Source	AgNO3	not reported · 0.5, 1, 2, 5 and 10 mM	2 · Section 1 · Experimental Methods
Solvent	acetonitrile	not reported	2 · Section 1 · Experimental Methods

Partial recipeSource: SI

Route 4: Other

2 · Section 1 · Experimental Methods

Metal precursorscommercial MIL-53 MOF (Al), Basolite A100

Linker precursorscommercial MIL-53 MOF (Al), Basolite A100

Solventsnone for activation

Additivesnone

Atmospherelow vacuum then Schlenk evacuation

Temperature180 C activation; room-temperature further evacuation

Time16 h at 180 C; further evacuation time not reported

Substrate orientationnot applicable

Oxidant / reductantnone

Work-upcommercial material used; activation under vacuum

Activationlow vacuum (10^-1 Torr) at 180 C for 16 h, then further evacuated at room temperature using Schlenk apparatus (10^-2 Torr)

Scalability contextCommercial powder; only activation reported, not primary MIL-53 synthesis.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	MIL-53 MOF (Al) (Basolite A100, Sigma-Aldrich)	approximately 100 mg	2 · Section 1 · Experimental Methods

Complete recipeSource: SI

Route 5: Other

2 · Section 1 · Experimental Methods

Metal precursorsRbOH, 16 mmol

Linker precursorsgamma-cyclodextrin, 2 mmol

Solvents40 mL deionized water; MeOH ca. 50 mL vapour diffusion; CH3CN wash/solvent exchange

Additivesnone reported

Atmosphereambient/not specified

Temperatureroom temperature/not specified

TimeMeOH vapour diffusion for 3-7 days; CH3CN solvent exchange for several days

Substrate orientationnot applicable

Oxidant / reductantnone reported

Work-upfiltered through 0.45 um PTFE syringe filter; filtrate divided into ten vials; crystals isolated and washed with CH3CN

Activationsolvent exchange in fresh CH3CN; degassing described separately before conductance measurements

Scalability contextTen-vial vapour diffusion batch; millimeter-sized crystals up to ~1.5 x 1.5 x 1 mm3.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	gamma-Cyclodextrin	2 mmol	2 · Section 1 · Experimental Methods
Metal Source	RbOH	16 mmol	2 · Section 1 · Experimental Methods
Solvent	deionized water	40 mL	2 · Section 1 · Experimental Methods
Solvent	MeOH	ca. 50 mL	2 · Section 1 · Experimental Methods
Solvent	CH3CN	not reported	2 · Section 1 · Experimental Methods