Synthesis · Semiconductive coordination networks from 2,3,6,7,10,11-hexakis(alkylthio) triphenylenes and bismuth(III) halides: Synthesis, structure-property relations, and solution processing

14 structured synthesis routes

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

Vague recipeSource: Main

Route 1: Unknown

4 · Crystallization of HMTT.BiCl3 (1)

Metal precursorsBiCl3

Linker precursorsHMTT

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	BiCl3	Not specified	4 · Crystallization of HMTT.BiCl3 (1)
Linker	HMTT	Not specified	4 · Crystallization of HMTT.BiCl3 (1)

Complete recipeSource: Main

Route 2: Drop Cast

5 · Solution Deposition of HMTT.BiCl3 (1) · Figure 12

Metal precursorsBiCl3

Linker precursorsHMTT

Solventsanhydrous 1,2-dichlorobenzene (DCB)

Atmosphereargon-filled glovebox followed by slight positive argon pressure and outflowing argon over the quartz disk

Temperature190 solution; 150 quartz disk

Timeabout 0.033 h solvent evaporation

Substrate orientationStrong orientation preference of [0 1 -1] plane in deposited crystallites

Work-upHot solution quickly pipetted onto heated quartz disk and solvent evaporated in about 2 min

Scalability contextPreliminary solution-processing test for device fabrication relevance.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTT	2.7 mg, 0.0053 mmol	5 · Solution Deposition of HMTT.BiCl3 (1) · Figure 12
Metal Source	BiCl3	2.0 mg, 0.0063 mmol	5 · Solution Deposition of HMTT.BiCl3 (1) · Figure 12
Solvent	1,2-dichlorobenzene (DCB), anhydrous	1.0 mL	5 · Solution Deposition of HMTT.BiCl3 (1) · Figure 12

Complete recipeSource: Main

Route 3: Solvothermal

4 · Crystallization of HMTT.BiBr3 (2)

Metal precursorsBiBr3

Linker precursorsHMTT

Solventsanhydrous DCB; benzene wash

Atmosphereargon protection

Temperatureabout 180

Timenot specified; heat-cool process repeated two more times

Work-upCooled to room temperature over about 30 min, repeated twice, filtered, washed with benzene under argon

Scalability context18.4 mg product; 87% based on HMTT.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTT	11.2 mg, 0.022 mmol	4 · Crystallization of HMTT.BiBr3 (2)
Metal Source	BiBr3	11.2 mg, 0.025 mmol	4 · Crystallization of HMTT.BiBr3 (2)
Solvent	anhydrous DCB	4 mL	4 · Crystallization of HMTT.BiBr3 (2)

Complete recipeSource: Main

Route 4: Solvothermal

4 · Crystallization of HMTT.BiBr3 (2)

Metal precursorsBiBr3

Linker precursorsHMTT

Solvents1,2-dichlorobenzene (DCB), anhydrous

Atmosphereargon-filled glovebox; tube sealed under vacuum

Temperature180

Time12

Work-upSlow cooling at 0.1 C/min to room temperature; dark-red blocklike crystals selected

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTT	9.2 mg, 0.018 mmol	4 · Crystallization of HMTT.BiBr3 (2)
Metal Source	BiBr3	9.0 mg, 0.020 mmol	4 · Crystallization of HMTT.BiBr3 (2)
Solvent	DCB (1,2-dichlorobenzene), anhydrous	0.6 mL	4 · Crystallization of HMTT.BiBr3 (2)

Complete recipeSource: Main

Route 5: Drop Cast

5 · Solution Deposition of HMTT.BiBr3 (2) · Figure S14

Metal precursorsBiBr3

Linker precursorsHMTT

Solventsanhydrous DCB

Atmospheresame argon-protected procedure as HMTT.BiCl3 deposition

Temperaturesame as HMTT.BiCl3 deposition (190 solution; 150 quartz disk)

Timeabout 0.033 h solvent evaporation by same procedure

Substrate orientationStrong orientation preference of [0 1 -1] plane

Work-upDropped onto quartz disk by same procedure as compound 1

Scalability contextPreliminary solution-processing test.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTT	2.9 mg, 0.0057 mmol	5 · Solution Deposition of HMTT.BiBr3 (2) · Figure S14
Metal Source	BiBr3	5.7 mg, 0.0127 mmol	5 · Solution Deposition of HMTT.BiBr3 (2) · Figure S14
Solvent	DCB, anhydrous	1.5 mL	5 · Solution Deposition of HMTT.BiBr3 (2) · Figure S14

Complete recipeSource: Main

Route 6: Solvothermal

4 · Crystallization of HMTT.2BiBr3 (3)

Metal precursorsBiBr3

Linker precursorsHMTT

Solventsanhydrous benzene; benzene wash

Atmospheresealed glass tube

Temperature120

Time120

Work-upCooled to room temperature at 0.1 C/min, filtered, washed with benzene

Scalability context29.5 mg product; 92% based on HMTT.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTT	11.5 mg, 0.023 mmol	4 · Crystallization of HMTT.2BiBr3 (3)
Metal Source	BiBr3	30.7 mg, 0.068 mmol	4 · Crystallization of HMTT.2BiBr3 (3)
Solvent	benzene, anhydrous	1.1 mL	4 · Crystallization of HMTT.2BiBr3 (3)

Complete recipeSource: Main

Route 7: Solvothermal

4 · Crystallization of HMTT.2BiBr3 (3)

Metal precursorsBiBr3

Linker precursorsHMTT

Solventsanhydrous benzene

Atmospheresealed under vacuum after liquid-nitrogen chilling

Temperature150

Time8

Work-upCrystallised in oil bath as dark red blocklike single crystals

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTT	18.6 mg, 0.037 mmol	4 · Crystallization of HMTT.2BiBr3 (3)
Metal Source	BiBr3	27.8 mg, 0.062 mmol	4 · Crystallization of HMTT.2BiBr3 (3)
Solvent	benzene, anhydrous	2.0 mL	4 · Crystallization of HMTT.2BiBr3 (3)

Complete recipeSource: Main

Route 8: Solvothermal

4 · Crystallization of HETT.2BiBr3 (4)

Metal precursorsBiBr3

Linker precursorsHETT

Solventsanhydrous toluene

Atmosphereclosed pressure tube

Temperature100

Time24

Work-upCooled to room temperature at 0.1 C/min

Scalability context47.5 mg product; 94% based on HETT.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HETT	20 mg, 0.034 mmol	4 · Crystallization of HETT.2BiBr3 (4)
Metal Source	BiBr3	39.6 mg, 0.088 mmol	4 · Crystallization of HETT.2BiBr3 (4)
Solvent	toluene, anhydrous	1 mL	4 · Crystallization of HETT.2BiBr3 (4)

Complete recipeSource: Main

Route 9: Solvothermal

4 · Crystallization of HETT.2BiBr3 (4)

Metal precursorsBiBr3

Linker precursorsHETT

Solventstoluene

Atmospheresealed under vacuum after liquid-nitrogen chilling

Temperature120

Time12

Work-upRed platelike crystals obtained during heating

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HETT	8.7 mg, 0.015 mmol	4 · Crystallization of HETT.2BiBr3 (4)
Metal Source	BiBr3	9.9 mg, 0.022 mmol	4 · Crystallization of HETT.2BiBr3 (4)
Solvent	toluene	0.6 mL	4 · Crystallization of HETT.2BiBr3 (4)

Complete recipeSource: Main

Route 10: Drop Cast

5 · Solution Deposition of HETT.2BiBr3 (4) · Figure 13

Metal precursorsBiBr3

Linker precursorsHETT

Solventsanhydrous benzene

Atmospheresimilar argon-protected solution-deposition procedure

Temperature90 solution and quartz disk

Timenot specified

Substrate orientationNo obvious orientation preference observed

Work-upHot benzene solution handled similarly and deposited onto heated quartz disk

Scalability contextPreliminary solution-processing test; high crystallinity and single phase reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HETT	3.2 mg, 0.0054 mmol	5 · Solution Deposition of HETT.2BiBr3 (4) · Figure 13
Metal Source	BiBr3	6.1 mg, 0.0136 mmol	5 · Solution Deposition of HETT.2BiBr3 (4) · Figure 13
Solvent	benzene, anhydrous	1.2 mL	5 · Solution Deposition of HETT.2BiBr3 (4) · Figure 13

Complete recipeSource: Main

Route 11: Solvothermal

5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)

Metal precursorsBiBr3

Linker precursorsHiPTT

Solventsanhydrous toluene

Atmosphereargon protection

Temperature100

Timenot specified; cooled over about 20 min

Work-upCooled to room temperature over about 20 min; orange-yellow crystals collected by vacuum filtration

Scalability context14.5 mg product; 65% based on HiPTT.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HiPTT	9.6 mg, 0.014 mmol	5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)
Metal Source	BiBr3	14.7 mg, 0.033 mmol	5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)
Solvent	toluene, anhydrous	0.6 mL	5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)

Complete recipeSource: Main

Route 12: Solvothermal

5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)

Metal precursorsBiBr3

Linker precursorsHiPTT

Solventstoluene

Atmospheresealed under vacuum after liquid-nitrogen chilling

Temperature100

Time2

Work-upCooled at 0.1 C/min to room temperature; orange-yellow blocklike crystals obtained

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HiPTT	19.6 mg, 0.029 mmol	5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)
Metal Source	BiBr3	14.4 mg, 0.032 mmol	5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)
Solvent	toluene	0.7 mL	5 · Crystallization of HiPTT.2BiBr3.C7H8 (5)

Complete recipeSource: Main

Route 13: Other

4 · Experimental Section · Scheme 1

Linker precursorshexabromotriphenylene (HBT); sodium thiomethoxide; iodoethane

Solventsanhydrous DMEU; water wash; CH2Cl2/hexane 1:4 silica column

Atmosphereargon

Temperaturerefluxing temperature approximately 240 C; then room temperature after iodoethane addition

Time6 h reflux; 0.5 h after iodoethane addition

Oxidant / reductantsodium thiomethoxide acts as thiolate source/demethylating reagent

Work-upPoured into water, filtered, washed with water, dried under vacuum, purified by silica gel column

Scalability contextReported 0.25 g, 100% based on HBT.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	hexabromotriphenylene (HBT)	0.30 g, 0.43 mmol	4 · Experimental Section · Scheme 1
Other	sodium thiomethoxide	0.76 g, 95%, 10.3 mmol	4 · Experimental Section · Scheme 1
Solvent	DMEU (1,3-dimethyl-2-imidazolidinone), anhydrous	40 mL	4 · Experimental Section · Scheme 1
Other	iodoethane	2.0 mL, 25 mmol, 99% purity	4 · Experimental Section · Scheme 1

Complete recipeSource: Main

Route 14: Other

4 · Experimental Section · Scheme 1

Linker precursorshexabromotriphenylene; sodium thiomethoxide; 2-iodopropane

Solventsanhydrous DMEU; toluene extraction; CH2Cl2/hexane 1:4 silica column

Atmosphereargon

Temperaturereflux, then cooled to 70 C before 2-iodopropane injection

Time6 h reflux; 1 h after 2-iodopropane addition

Oxidant / reductantsodium thiomethoxide acts as thiolate source/demethylating reagent

Work-upPoured into ice water, extracted with toluene, washed with water and brine, dried over sodium sulfate, evaporated in vacuo, silica gel purification

Scalability contextReported 0.38 g, 99% based on HBT.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	hexabromotriphenylene	0.40 g, 0.57 mmol	4 · Experimental Section · Scheme 1
Other	sodium thiomethoxide	1.00 g, 95%, 13.6 mmol	4 · Experimental Section · Scheme 1
Solvent	DMEU, anhydrous	40 mL	4 · Experimental Section · Scheme 1
Other	2-iodopropane	2.8 mL, 27.7 mmol, 99% purity	4 · Experimental Section · Scheme 1