Synthesis · Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing

9 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Drop Cast

S34 · Fabrication of sensing devices · Figure S33

Metal precursorspreformed Bi(HHTP)

Linker precursorspreformed Bi(HHTP)

Solventsdeionized water

Additivesnone

Atmosphereambient drying

Temperatureroom temperature

Time1 h sonication; 16-18 h drying

Substrate orientation10 um gap gold interdigitated electrodes

Oxidant / reductantnone

Work-updry in dark ambient atmosphere

Activationequilibrated under N2 for 1 h before sensing

Scalability contextFive devices shown; typical devices used 10 uL dropcast suspension.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Bi(HHTP) powder	1.5 mg in 1 mL; 10 uL dropcast · 1.5 mg/mL	S34 · Fabrication of sensing devices · Figure S33
Solvent	deionized water	1 mL	S34 · Fabrication of sensing devices · Figure S33

Complete recipeSource: SI

Route 2: Hydrothermal

S7-S8 · Reaction Optimization Procedures · Figure S5

Metal precursorsBi(OAc)3

Linker precursorsHHTP

SolventsDI H2O; ethyl acetate for Soxhlet/activation where specified

Additivesnone

Atmospherenot specified / open atmosphere for trace 4

Temperature85 C reaction; optional 50 C water wash; Soxhlet EtOAc at 165 C where specified

Time24 h reaction; additional purification time varies by trace

Oxidant / reductantnone

Work-updry in vacuum desiccator overnight before pXRD; no purification before trace

Activationvaries by optimisation trace; see notes

Scalability context20 mg HHTP (0.062 mmol); small-scale 2:1 route

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	20 mg HHTP (0.062 mmol)	S7-S8 · Reaction Optimization Procedures · Figure S5
Metal Source	Bi(OAc)3	46 mg (0.119 mmol)	S7-S8 · Reaction Optimization Procedures · Figure S5
Solvent	DI H2O	40 mL · [1.5 M] as printed in SI	S7-S8 · Reaction Optimization Procedures · Figure S5

Complete recipeSource: SI

Route 3: Hydrothermal

S7-S8 · Reaction Optimization Procedures · Figure S5

Metal precursorsBi(OAc)3

Linker precursorsHHTP

SolventsDI H2O; ethyl acetate for Soxhlet/activation where specified

Additivesnone

Atmospherenot specified / open atmosphere for trace 4

Temperature85 C reaction; optional 50 C water wash; Soxhlet EtOAc at 165 C where specified

Time24 h reaction; additional purification time varies by trace

Oxidant / reductantnone

Work-upSoxhlet extraction in EtOAc for one week at 165 C, then vacuum desiccator 18 h

Activationvaries by optimisation trace; see notes

Scalability contextmaterial from trace 1; purification-only optimisation

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	material from trace 1	S7-S8 · Reaction Optimization Procedures · Figure S5
Metal Source	Bi(OAc)3	same as trace 1	S7-S8 · Reaction Optimization Procedures · Figure S5
Solvent	DI H2O	same as trace 1 · [1.5 M] as printed in SI	S7-S8 · Reaction Optimization Procedures · Figure S5

Complete recipeSource: SI

Route 4: Hydrothermal

S7-S8 · Reaction Optimization Procedures · Figure S5

Metal precursorsBi(OAc)3

Linker precursorsHHTP

SolventsDI H2O; ethyl acetate for Soxhlet/activation where specified

Additivesnone

Atmospherenot specified / open atmosphere for trace 4

Temperature85 C reaction; optional 50 C water wash; Soxhlet EtOAc at 165 C where specified

Time24 h reaction; additional purification time varies by trace

Oxidant / reductantnone

Work-upvacuum desiccator overnight; Soxhlet one week; then 100 mL DI H2O at 50 C for two days if Bi(OAc)3 remained

Activationvaries by optimisation trace; see notes

Scalability context80 mg HHTP (0.247 mmol); scaled 2:1 route

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	80 mg HHTP (0.247 mmol)	S7-S8 · Reaction Optimization Procedures · Figure S5
Metal Source	Bi(OAc)3	184 mg (0.477 mmol)	S7-S8 · Reaction Optimization Procedures · Figure S5
Solvent	DI H2O	160 mL reaction; 100 mL DI H2O post-Soxhlet wash · [1.5 M] as printed in SI	S7-S8 · Reaction Optimization Procedures · Figure S5

Complete recipeSource: Both

Route 5: Hydrothermal

S5-S6 · 1.3 Procedure 1 · Figure S4

Metal precursorsBi(OAc)3

Linker precursorsHHTP

SolventsH2O; DI H2O; ethyl acetate

Additivesnone

Atmosphereopen atmosphere

Temperature85 C reaction; 50 C water wash; vacuum oven after activation

Time24 h reaction; 24 h water wash; 3 days EtOAc activation; 24 h vacuum oven

Oxidant / reductantnone

Work-upcentrifuge 6000 rpm 5 min, decant, suspend in 200 mL DI H2O at 50 C 24 h with water exchange after 6 h, centrifuge/decant, vacuum desiccator overnight

Activation40 mL EtOAc, vortex 30 s, stand 3 days with daily solvent exchange and vortexing; vacuum oven 24 h before sensing

Scalability context2:1 metal:ligand route; main text reports residual Bi(OAc)3 can be removed by purification.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	100 mg (0.308 mmol)	S5-S6 · 1.3 Procedure 1 · Figure S4
Metal Source	Bi(OAc)3	238 mg (0.616 mmol)	S5-S6 · 1.3 Procedure 1 · Figure S4
Solvent	H2O	200 mL reaction; 200 mL DI H2O wash	S5-S6 · 1.3 Procedure 1 · Figure S4
Solvent	ethyl acetate	40 mL	S5-S6 · 1.3 Procedure 1 · Figure S4

Complete recipeSource: Both

Route 6: Hydrothermal

S6 · 1.4 Procedure 2

Metal precursorsBi(OAc)3

Linker precursorsHHTP

SolventsH2O; DI H2O; ethyl acetate

Additivesnone

Atmosphereopen atmosphere

Temperature85 C reaction; 50 C water wash; vacuum oven after activation

Time24 h reaction; 24 h water wash; 3 days EtOAc activation; 24 h vacuum oven

Oxidant / reductantnone

Work-upcentrifuge 6000 rpm 5 min, decant, suspend in 100 mL DI H2O at 50 C 24 h with water exchange after 6 h, centrifuge/decant, vacuum desiccator overnight

Activation40 mL EtOAc, vortex 30 s, stand 3 days with daily solvent exchange and vortexing; vacuum oven 24 h before sensing

Scalability context1:1 metal:ligand route avoids residual Bi(OAc)3; used for sensing devices in SI.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	100 mg (0.308 mmol)	S6 · 1.4 Procedure 2
Metal Source	Bi(OAc)3	119 mg (0.308 mmol)	S6 · 1.4 Procedure 2
Solvent	H2O	200 mL reaction; 100 mL DI H2O wash	S6 · 1.4 Procedure 2
Solvent	ethyl acetate	40 mL	S6 · 1.4 Procedure 2

Partial recipeSource: SI

Route 7: Drop Cast

S27 · Optical absorbance Band Gap Calculation · Figure S28

Metal precursorspreformed Bi(HHTP)

Linker precursorspreformed Bi(HHTP)

Solventsnot explicitly specified for suspension

Additivesnone

Atmosphereambient

Temperatureroom temperature

Time5 min sonication

Substrate orientationquartz cuvette

Oxidant / reductantnone

Work-updrop cast to transparent thin film

Activationnone

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	Bi(HHTP)	10 mg in 2 mL	S27 · Optical absorbance Band Gap Calculation · Figure S28

Complete recipeSource: SI

Route 8: Other

S4 · 1.2 Synthesis of HHTP · Figure S2

Metal precursorsnone

Linker precursorsHMTP

Solventsdichloromethane; DI water; brine; ethyl acetate

AdditivesBBr3; dilute sulfuric acid

Atmosphereinert atmosphere during BBr3 addition

Temperature0 C addition; room temperature overnight; 75 C 12 h; 50 C 8 h; dry at 52 C

Time20 h + 12 h + 8 h

Oxidant / reductantBBr3 demethylation reagent

Work-upwater quench, brine, EtOAc, heat biphasic solution, acidify, filter, reduced-pressure dry

Activationnone

Scalability context1.81 g HHTP, 76% yield

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTP	3.01 g (7.35 mmol)	S4 · 1.2 Synthesis of HHTP · Figure S2
Reductant	boron tribromide	5.2 mL (51.45 mmol)	S4 · 1.2 Synthesis of HHTP · Figure S2
Solvent	dichloromethane	25 mL	S4 · 1.2 Synthesis of HHTP · Figure S2
Solvent	DI water	30 mL quench	S4 · 1.2 Synthesis of HHTP · Figure S2
Solvent	brine	25 mL	S4 · 1.2 Synthesis of HHTP · Figure S2
Solvent	ethyl acetate	100 mL	S4 · 1.2 Synthesis of HHTP · Figure S2
Acid	dilute sulfuric acid	not specified · dilute	S4 · 1.2 Synthesis of HHTP · Figure S2

Complete recipeSource: SI

Route 9: Other

S3-S4 · 1.1 Synthesis of HMTP · Figure S1

Metal precursorsnone

Linker precursorsveratrole

Solventsdichloromethane; methanol quench/wash

AdditivesFeCl3; concentrated sulfuric acid

Atmospherenot specified

Temperature0 C addition; room temperature over 3 h; dry at 52 C

Time3 h plus 30 min after methanol quench

Oxidant / reductantFeCl3 oxidant

Work-upmethanol quench, filtration, methanol wash 5 x 50 mL, reduced-pressure drying

Activationnone

Scalability context64.3 g product, 64% yield

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	veratrole	9.2 mL (72.4 mmol)	S3-S4 · 1.1 Synthesis of HMTP · Figure S1
Oxidant	FeCl3	35.2 g (217.2 mmol)	S3-S4 · 1.1 Synthesis of HMTP · Figure S1
Acid	concentrated sulfuric acid	0.75 mL	S3-S4 · 1.1 Synthesis of HMTP · Figure S1
Solvent	dichloromethane	50 mL + 100 mL	S3-S4 · 1.1 Synthesis of HMTP · Figure S1
Solvent	methanol	150 mL quench; 5 x 50 mL wash	S3-S4 · 1.1 Synthesis of HMTP · Figure S1