Synthesis · Conductive, Large-Area, and Continuous 7,7,8,8-Tetracyanoquinodimethane@HKUST-1 Thin Films Fabricated Using Solution Shearing

3 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solution Shearing

10203-10204 · Experimental Section · Figure 1

Metal precursorscopper(II) nitrate hemi(pentahydrate) (5.25 mmol)

Linker precursorstrimesic acid / H3BTC (2.76 mmol)

Solventsdimethyl sulfoxide (64.0 mmol); methanol for glass cleaning; toluene/acetone/isopropyl alcohol for blade cleaning; OTS in toluene for blade treatment

Additives0.1 wt % trichloro(octadecyl)silane (OTS) in toluene for hydrophobic coating blade functionalisation

Atmosphereambient processing not otherwise specified; electrical metal evaporation later performed in glove box

Temperature160 for shearing; coating blade OTS treatment at 50 overnight

Timesolution shearing crystallisation within a minute; 60 s between repeated passes; glass sonication 15 min; UV-ozone at least 10 min; blade OTS treatment overnight

Substrate orientationglass slides ca. 0.5 x 1 inch fixed to bottom vacuum stage; silicon wafer coating blade fixed to top vacuum stage; blade angle/height manually controlled

Work-upglass substrate sonicated in methanol and UV-ozone cleaned; coating blade rinsed, UV-ozone cleaned, OTS-treated, and sonicated in acetone; after each cycle substrate left on heated stage 60 s before next pass

Activationnone for pristine film; solvent-exchange or thermal activation used before TCNQ loading in separate routes

Scalability contextLarge-area (> cm2), continuous thin films reported; four cycles reached 99 +/- 0.6% coverage and thickness 5.4 +/- 0.8 um.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper(II) nitrate hemi(pentahydrate)	5.25 mmol	10203-10204 · Experimental Section · Figure 1
Solvent	dimethyl sulfoxide (DMSO)	64.0 mmol	10203-10204 · Experimental Section · Figure 1
Linker	trimesic acid (H3BTC)	2.76 mmol	10203-10204 · Experimental Section · Figure 1
Other	HKUST-1 precursor solution injected into blade/substrate gap	3-8 uL per pass	10203-10204 · Experimental Section · Figure 1
Additive	trichloro(octadecyl)silane (OTS) in toluene	0.1 wt %	10203-10204 · Experimental Section · Figure 1

Complete recipeSource: Main

Route 2: Other

10204-10205 · Experimental Section; Results and Discussion

Metal precursorspreformed solution-sheared HKUST-1 thin film

Linker precursorsHKUST-1 BTC linkers; TCNQ guest molecule

Solventsanhydrous dichloromethane (CH2Cl2) for solvent exchange and TCNQ solution

AtmosphereTCNQ solution prepared in moisture-free nitrogen-charged glove box

Temperature40 after solvent exchange to remove solvent residue

TimeCH2Cl2 soak 20 h, fresh CH2Cl2 wash 4 h, heat 40 deg C for 2 h, then TCNQ soak for desired periods up to 480 h

Substrate orientationsolution-sheared HKUST-1 thin film on glass substrate

Oxidant / reductantTCNQ redox-active guest; no separate oxidant/reductant reported

Work-upsoaked in pure anhydrous dichloromethane, washed again with new pure anhydrous dichloromethane, heated at 40 deg C for 2 h, immediately transferred to TCNQ solution

Activationsolvent exchange with anhydrous CH2Cl2 to remove solvent residue/water and create open metal sites while limiting Cu(II) reduction

Scalability contextApplied to four-cycle large-area continuous HKUST-1 thin films used for conductivity measurements.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	solution-sheared HKUST-1 thin film	Not specified	10204-10205 · Experimental Section; Results and Discussion
Solvent	anhydrous dichloromethane	20 mL for TCNQ solution; pure solvent for 20 h soak plus 4 h fresh wash	10204-10205 · Experimental Section; Results and Discussion
Additive	TCNQ	60 mg · 60 mg in 20 mL anhydrous dichloromethane	10204-10205 · Experimental Section; Results and Discussion

Complete recipeSource: Both

Route 3: Other

10204 · Experimental Section

Metal precursorspreformed solution-sheared HKUST-1 thin film

Linker precursorsHKUST-1 BTC linkers; TCNQ guest molecule

Solventsanhydrous dichloromethane for TCNQ solution

Atmospherevacuum oven for thermal treatment; TCNQ solution prepared in nitrogen glove box

Temperature120 then 180

Time120 deg C for 10 h, then 180 deg C for 2 h, then TCNQ soak for desired period

Substrate orientationsolution-sheared HKUST-1 thin film on glass substrate

Oxidant / reductantTCNQ guest; thermal treatment causes partial Cu(II) reduction to Cu(I) according to XPS

Work-upheated in vacuum oven then immediately transferred to TCNQ solution

Activationthermal activation in vacuum oven

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	solution-sheared HKUST-1 thin film	Not specified	10204 · Experimental Section
Additive	TCNQ	60 mg · 60 mg in 20 mL anhydrous dichloromethane	10204 · Experimental Section
Solvent	anhydrous dichloromethane	20 mL	10204 · Experimental Section