Synthesis · Nanorods of a novel highly conductive 2D metal-organic framework based on perthiolated coronene for thermoelectric conversion

4 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

2 · Synthesis of Ni-PTC nanorod

Metal precursorsNi(OAc)2.4H2O

Linker precursorsPTC

SolventsDeoxygenated chlorobenzene and ethanol mixture

AtmosphereDeoxygenated solvents; SI does not explicitly state an inert headspace for the Ni-PTC reaction.

Temperature80

Time36

Work-upCollected as dark powder and washed with ethanol, water and ethyl ether.

ActivationDried under vacuum at 60 deg C overnight.

Scalability contextBench-scale homogeneous solution reaction from 68 mg PTC and 75 mg nickel acetate tetrahydrate.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PTC	68 mg, 0.1 mmol	2 · Synthesis of Ni-PTC nanorod
Metal Source	Ni(OAc)2.4H2O	75 mg, 0.3 mmol	2 · Synthesis of Ni-PTC nanorod
Solvent	deoxygenated chlorobenzene and ethanol	30 mL	2 · Synthesis of Ni-PTC nanorod

Complete recipeSource: SI

Route 2: Other

1-2 · Synthesis of PBTC

Linker precursorsPCC, benzyl mercaptan

SolventsAnhydrous DMF; toluene workup; dichloromethane/hexane=1/1 chromatography eluent

AdditivesSodium hydride; saturated Na2CO3 solution; MgSO4 drying agent

AtmosphereArgon

Temperature0

Time5.5

Oxidant / reductantNaH base/reductant

Work-upToluene and saturated Na2CO3 added; organic phases washed twice, dried over MgSO4, filtered, solvent evaporated; silica gel chromatography; last fraction collected.

ActivationDried under vacuum.

Scalability context318.0 mg PBTC obtained in 90% yield.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Base	sodium hydride	120.0 mg, 5.0 mmol	1-2 · Synthesis of PBTC
Solvent	anhydrous DMF	10.0 mL	1-2 · Synthesis of PBTC
Linker	benzyl mercaptan	596.0 mg, 4.8 mmol	1-2 · Synthesis of PBTC
Linker	PCC	143 mg, 0.2 mmol	1-2 · Synthesis of PBTC
Solvent	toluene	50 mL	1-2 · Synthesis of PBTC
Additive	saturated Na2CO3 solution	100 mL · saturated	1-2 · Synthesis of PBTC

Complete recipeSource: SI

Route 3: Other

1 · Synthesis of PBTC

Linker precursorsCoronene

SolventsCCl4; methanol quench

AdditivesAlCl3, ICl

Temperature81

Time48

Oxidant / reductantICl chlorination reagent

Work-upPoured into 50 mL methanol; filtered; washed with methanol, 1 M hydrochloric acid, water and acetone.

ActivationDried in vacuum at 60 deg C overnight.

Scalability context0.97 g PCC obtained in 85% yield from 480 mg coronene.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	coronene	1.6 mmol (480.0 mg)	1 · Synthesis of PBTC
Additive	AlCl3	3.2 mmol (426.0 mg)	1 · Synthesis of PBTC
Oxidant	ICl	192 mmol (15.0 g)	1 · Synthesis of PBTC
Solvent	CCl4	40 mL	1 · Synthesis of PBTC

Complete recipeSource: Both

Route 4: Other

2 · Synthesis of perthiolated coronene (PTC)

Linker precursorsPBTC

SolventsAnhydrous fluorobenzene; methanol; n-hexane and cold fluorobenzene washes; deoxygenated water wash

AdditivesBBr3

AtmosphereArgon

Temperature0 then reflux

Time12

Oxidant / reductantBBr3 Lewis acid dealkylation

Work-upFiltered after 12 h, washed with n-hexane and cold fluorobenzene; dithiaborole intermediate treated with MeOH under argon; red product filtered, washed with deoxygenated water and MeOH twice.

ActivationDried in vacuum at 60 deg C for 1 h.

Scalability context68 mg PTC from 176 mg PBTC; almost quantitative yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PBTC	176 mg, 0.1 mmol	2 · Synthesis of perthiolated coronene (PTC)
Solvent	anhydrous fluorobenzene	10.0 mL	2 · Synthesis of perthiolated coronene (PTC)
Acid	pure BBr3	0.12 ml, 1.2 mmol	2 · Synthesis of perthiolated coronene (PTC)
Solvent	MeOH	30 mL	2 · Synthesis of perthiolated coronene (PTC)