Synthesis · Bromine Vapor Induced Continuous p- to n-Type Conversion of a Semiconductive Metal-Organic Framework Cu[Cu(pdt)2]

3 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Other

2 · Experimental Section - Bromine Vapor Doping · Figure S2

Metal precursorsCu[Cu(pdt)2] polycrystalline powder (100 mg)

Linker precursorspdt in preformed Cu[Cu(pdt)2]

Solventsnone for doping; bromine vapour injected

AdditivesBr2 vapour, variable volume

AtmosphereN2 after three pump-purge cycles

Temperature60 deg C anneal after room-temperature Br2 vapour exposure

Time24 h anneal after doping; exposure time not specified

Oxidant / reductantBr2 vapour acts as oxidant

Work-upSamples transferred to screw vials after doping.

ActivationAnnealed for 24 h at 60 deg C.

Scalability contextDoping performed using 100 mg MOF at a time; upper Br loading about x = 1 even under excess vapour.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu[Cu(pdt)2]	100 mg	2 · Experimental Section - Bromine Vapor Doping · Figure S2
Oxidant	bromine vapour (Br2)	different volumes; not specified · vapour, not liquid	2 · Experimental Section - Bromine Vapor Doping · Figure S2
Other	N2	pump-purge three times	2 · Experimental Section - Bromine Vapor Doping · Figure S2

Complete recipeSource: Main

Route 2: Other

2 · Experimental Section - Synthesis of Cu[Cu(pdt)2]

Metal precursorsNa[Cu(pdt)2].2H2O (1.0 g, 2.5 mmol); CuI (0.45 g, 2.3 mmol)

Linker precursorspdt already present in Na[Cu(pdt)2].2H2O

SolventsCH3CN, 500 mL for Na[Cu(pdt)2].2H2O solution plus 100 mL for CuI solution

Additivesnone reported

Atmospherenot specified

Temperatureroom temperature

Time0.5 h stirring after dropwise CuI addition; vacuum drying overnight

Oxidant / reductantCuI reagent; no separate oxidant/reductant reported

Work-upSolution filtered; CuI solution added dropwise; black polycrystalline solid collected using membrane filter.

ActivationDried under vacuum overnight before characterisation.

Scalability contextReported on 1.0 g Na[Cu(pdt)2].2H2O precursor scale.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Na[Cu(pdt)2].2H2O	1.0 g, 2.5 mmol	2 · Experimental Section - Synthesis of Cu[Cu(pdt)2]
Metal Source	CuI	0.45 g, 2.3 mmol	2 · Experimental Section - Synthesis of Cu[Cu(pdt)2]
Solvent	CH3CN	500 mL + 100 mL	2 · Experimental Section - Synthesis of Cu[Cu(pdt)2]

Partial recipeSource: Main

Route 3: Other

2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O

Metal precursorsCu(ClO4)2.6H2O (1.84 g, 5 mmol)

Linker precursorsH2pdt (1.44 g, 10 mmol), prepared following an earlier procedure

Solvents300 mL deionised water; 300 mL MeOH

AdditivesNaOH (0.8 g, 20 mmol); NaBr (2 g)

Atmospherenot specified

Temperatureroom temperature / not specified

Timeuntil colour changes; not fully specified

Oxidant / reductantH2O2 (0.6 mL, 30%)

Work-upDark green precipitate collected by filtration and washed with H2O.

Activationnone reported for precursor

Scalability contextGram-scale precursor quantities reported.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Base	NaOH	0.8 g, 20 mmol	2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O
Linker	H2pdt	1.44 g, 10 mmol	2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O
Metal Source	Cu(ClO4)2.6H2O	1.84 g, 5 mmol	2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O
Solvent	deionised water	300 mL	2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O
Solvent	MeOH	300 mL	2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O
Additive	NaBr	2 g	2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O
Oxidant	H2O2	0.6 mL · 30%	2 · Experimental Section - Synthesis of Na[Cu(pdt)2].2H2O