Synthesis · Conductive Hybrid Cu-HHTP-TCNQ Metal–Organic Frameworks for Chemiresistive Sensing

6 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

8 · Experimental Section / Fabrication of Chips with Prepatterned Electrodes · Figure 4a-c

Metal precursorsTi and Au evaporated electrodes

SolventsDimethylsulfoxide for lift-off; phosphoric acid for oxide etch

AdditivesAZ2020nlof and AZ1505 photoresists; Al2O3 passivation

Temperature110 soft bake; 55 oxide etch

TimeElectrode fabrication multistep; MOF film standard synthesis at 45 min for representative device

Substrate orientationFused silica/glass chip with central contacts and outer gold pads; Al2O3 insulating layer between chip and film.

Work-upUV lithography, Ti/Au evaporation, lift-off, plasma-enhanced ALD Al2O3, wet etching of contact/probe openings, wafer dicing.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	fused silica wafer	4 inches, 500 um thickness	8 · Experimental Section / Fabrication of Chips with Prepatterned Electrodes · Figure 4a-c
Other	AZ2020nlof resist	spin-coated 4000 rpm, 40 s	8 · Experimental Section / Fabrication of Chips with Prepatterned Electrodes · Figure 4a-c
Other	Ti/Au	Ti 5 nm; Au 50 nm	8 · Experimental Section / Fabrication of Chips with Prepatterned Electrodes · Figure 4a-c
Other	Al2O3	50 nm · plasma-enhanced atomic layer deposition	8 · Experimental Section / Fabrication of Chips with Prepatterned Electrodes · Figure 4a-c
Acid	phosphoric acid	85%, 55 C for 105 s · 85%	8 · Experimental Section / Fabrication of Chips with Prepatterned Electrodes · Figure 4a-c

Vague recipeSource: Main

Route 2: Liquid Liquid Interface

3 · 2.1. Synthesis

Metal precursorsaqueous Cu(II) nitrate solution

Linker precursorsHHTP only; TCNQ omitted

Solventswater; ethyl acetate

Atmosphereargon-sealed vial, reaction at 0 C

Temperature0

Time1

Substrate orientationnone reported

Oxidant / reductantnone reported

Work-upnot reported for control powder

Activationnot reported

Scalability contextControl showed slow formation of nonconnected MOF powder after 1 h, not a continuous film.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(II) nitrate solution	2 mL · 10 mM	3 · 2.1. Synthesis
Linker	HHTP	1 mL in ethyl acetate · 0.4 mM	3 · 2.1. Synthesis
Solvent	water	2 mL	3 · 2.1. Synthesis
Solvent	ethyl acetate	1 mL	3 · 2.1. Synthesis

Complete recipeSource: Both

Route 3: Liquid Liquid Interface

8 · Experimental Section / Grazing-Incidence Small-Angle X-Ray Scattering · Figure S7

Metal precursorsCu(NO3)2*xH2O

Linker precursorsHHTP; TCNQ

SolventsWater; ethyl acetate

AtmosphereArgon-filled sealed vial for standard procedure; GI-SAXS performed in vacuum (~0.01 mbar)

Temperature0

Time0.667

Substrate orientationDeposited onto Si(100) wafer, 500 um thick with 285 nm native SiO2; water rinse and 5 min air plasma before placement.

Work-upStandard interfacial film growth and deposition onto silicon wafer.

Complete recipeSource: Both

Route 4: Liquid Liquid Interface

8 · Experimental Section / Synthesis of Cu-HHTP-TCNQ Films · Figure 1; SI Video information

Metal precursorsCu(NO3)2*xH2O; aqueous Cu(II) nitrate solution

Linker precursorsHHTP in ethyl acetate; TCNQ in ethyl acetate

SolventsWater; ethyl acetate; acetone and isopropyl alcohol for washing

AtmosphereArgon-filled sealed vial; all solvents degassed with argon before use

Temperature0

Time0.167-1.333 (10-80 min series); visible within 1 min; black by 15 min

Substrate orientationSubstrate of choice placed at the bottom of vial before reaction; film sinks onto substrate when liquids are removed.

Work-upStop by carefully removing all liquid with a syringe; sink film onto substrate; dry in air; wash deposited film in acetone and isopropyl alcohol; dry again in air.

ActivationNo separate activation reported.

Scalability contextContinuously grown film lateral dimension defined by reaction vial, about 5 cm2.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*Cu(NO3)2xH2O**	2 mL · 10 mm aqueous Cu(II) nitrate solution	8 · Experimental Section / Synthesis of Cu-HHTP-TCNQ Films · Figure 1; SI Video information
Linker	HHTP (Triphenylene-2,3,6,7,10,11-hexaol; 98%)	1 mL solution · 0.4 mm in ethyl acetate	8 · Experimental Section / Synthesis of Cu-HHTP-TCNQ Films · Figure 1; SI Video information
Linker	TCNQ (7,7,8,8-Tetracyanoquinodimethane)	1 mL solution · 4 mm in ethyl acetate	8 · Experimental Section / Synthesis of Cu-HHTP-TCNQ Films · Figure 1; SI Video information
Solvent	ethyl acetate	degassed with argon	8 · Experimental Section / Synthesis of Cu-HHTP-TCNQ Films · Figure 1; SI Video information
Solvent	acetone	wash solvent	8 · Experimental Section / Synthesis of Cu-HHTP-TCNQ Films · Figure 1; SI Video information
Solvent	isopropyl alcohol	wash solvent	8 · Experimental Section / Synthesis of Cu-HHTP-TCNQ Films · Figure 1; SI Video information

Complete recipeSource: Both

Route 5: Liquid Liquid Interface

8 · Experimental Section / Transmission Electron Microscopy · Figure S6

Metal precursorsCu(NO3)2*xH2O

Linker precursorsHHTP; TCNQ

SolventsWater; ethyl acetate

AtmosphereArgon-filled sealed vial for standard procedure

Temperature0

Time0.667

Substrate orientationFilm fished onto copper TEM grid

Work-upStandard interfacial film growth, then transfer to TEM grid.

Complete recipeSource: Main

Route 6: Liquid Liquid Interface

8 · Experimental Section / X-Ray Diffraction · Figure 3f,g

Metal precursorsCu(NO3)2*xH2O

Linker precursorsHHTP; TCNQ

SolventsWater; ethyl acetate

AtmosphereArgon-filled sealed vial for standard procedure

Temperature0

Time0.75

Substrate orientationRepeated films merged as powder for XRD

Work-upRepeated syntheses and subsequent merging to obtain larger powder amount.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*Cu(NO3)2xH2O**	standard interfacial procedure	8 · Experimental Section / X-Ray Diffraction · Figure 3f,g
Linker	HHTP	standard interfacial procedure	8 · Experimental Section / X-Ray Diffraction · Figure 3f,g
Linker	TCNQ	standard interfacial procedure	8 · Experimental Section / X-Ray Diffraction · Figure 3f,g