Synthesis · From n- To p-Type Material: Effect of Metal Ion on Charge Transport in Metal-Organic Materials

4 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

p003 · a-Pd-HITP powder

Metal precursorsK2PdCl6 (88.1 mg, 0.269 mmol, 1.5 equiv.)

Linker precursorsHATP*6HCl (95.0 mg, 0.177 mmol, 1 equiv.)

SolventsDI water (22.0 mL for linker solution; 12.0 mL for palladium solution); washed/dried using previous procedure

AdditivesNH4OH (1.01 mL, 14.6 mmol, 83 equiv.)

AtmosphereAir bubbling for 45 min followed by nitrogen bubbling for 2 h.

Temperature65

Time0.75 h air bubbling + 2 h nitrogen bubbling

Oxidant / reductantAir during synthesis; palladium chloride salt provides metal and chloride.

Work-upWashed and dried using the previous Ni/Pt procedure.

ActivationPorosity sample associated with the same activation protocol used for MOG analogues.

Scalability contextBatch yielded 56.8 mg clumpy black powder.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	*HATP 6HCl**	95.0 mg, 0.177 mmol, 1 equiv.	p003 · a-Pd-HITP powder
Metal Source	K2PdCl6	88.1 mg, 0.269 mmol, 1.5 equiv.	p003 · a-Pd-HITP powder
Solvent	DI water	22.0 mL + 12.0 mL	p003 · a-Pd-HITP powder
Base	NH4OH	1.01 mL, 14.6 mmol, 83 equiv.	p003 · a-Pd-HITP powder
Oxidant	air	bubbled 45 minutes	p003 · a-Pd-HITP powder
Other	nitrogen	bubbled 2 hours	p003 · a-Pd-HITP powder

Complete recipeSource: Both

Route 2: Other

p002 · Syntheses

Metal precursors(NH4)2PtCl6 (105.4 mg, 0.404 mmol, 1.5 equiv.)

Linker precursorsHATP*6HCl (141.7 mg, 0.263 mmol, 1 equiv.)

SolventsDI water (20.0 mL for linker solution; 30.0 mL for platinum solution); wash and activation solvents as previous procedure

AdditivesNH4OH (1.50 mL, 21.8 mmol, 83 equiv.)

AtmosphereAir bubbling for 45 min followed by nitrogen bubbling for 2 h.

Temperature65

Time0.75 h air bubbling + 2 h nitrogen bubbling; activation includes 100 C vacuum hold for 6 h

Oxidant / reductantAir during synthesis; platinum chloride salt provides metal and chloride.

Work-upWashed and dried using the Ni-HITP procedure.

ActivationSame pore-clearing and vacuum activation procedure as adsorption samples: water and ethanol soaks followed by dynamic vacuum and 100 C hold.

Scalability contextBatch used 0.263 mmol linker and yielded 94.8 mg clumpy black powder.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	*HATP6HCl**	141.7 mg, 0.263 mmol, 1 equiv.	p002 · Syntheses
Metal Source	(NH4)2PtCl6	105.4 mg, 0.404 mmol, 1.5 equiv.	p002 · Syntheses
Solvent	DI water	20.0 mL + 30.0 mL	p002 · Syntheses
Base	NH4OH	1.50 mL, 21.8 mmol, 83 equiv.	p002 · Syntheses
Oxidant	air	bubbled 45 min	p002 · Syntheses
Other	nitrogen	bubbled 2 h	p002 · Syntheses

Complete recipeSource: SI

Route 3: Other

p002-p003 · Synthesis of HATP*6HCl · Scheme S1

Metal precursorsPd2(dba)3 catalyst (1.29 g, 1.40 mmol, 0.25 eq.) for protected amination step

Linker precursorsTriphenylene 1; hexabromotriphenylene 2; benzophenone imine

SolventsNitrobenzene, toluene, dichloromethane, 30% EtOAc/Hex, THF

AdditivesFe0, Br2, rac-BINAP, NaOtBu, concentrated aqueous HCl

AtmosphereAr-flushed bromination; glovebox and argon balloon for amination; nitrogen-flushed vial and nitrogen bubbling for deprotection.

Temperature180 for bromination reflux; 110 for amination; room temperature for HCl deprotection

Time2 h bromination reflux; 14 h amination; 50 min N2 bubbling during deprotection; 16 h vacuum drying

Oxidant / reductantBr2 bromination; acid deprotection with concentrated HCl.

Work-upVacuum filtration; chromatography and recrystallisation for protected intermediate; THF washing and centrifugation for HATP*6HCl.

ActivationDried under vacuum for 16 h.

Scalability contextHATP*6HCl step gave 160 mg, 77% from 500 mg protected intermediate.

Show 9 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	triphenylene 1	11.940 g, 52.12 mmol, 1.0 eq	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Oxidant	Br2	23.8 mL	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Additive	Fe0	1.08 g, 19.16 mmol, 0.37 eq	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Solvent	nitrobenzene	430 mL	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Other	Pd2(dba)3	1.29 g, 1.40 mmol, 0.25 eq.	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Additive	rac-BINAP	1.75 g, 2.81 mmol, 0.5 eq.	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Base	NaOtBu	4.32 g, 44.9 mmol, 8.0 eq.	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Acid	concentrated aqueous HCl	0.63 mL, 7.7 mmol, 20 equiv	p002-p003 · Synthesis of HATP*6HCl · Scheme S1
Solvent	THF	15.0 mL plus 3 x 3 mL washes	p002-p003 · Synthesis of HATP*6HCl · Scheme S1

Complete recipeSource: Both

Route 4: Other

p002-p003 · Syntheses; Porosity method

Metal precursorsNiCl2*6H2O (95.7 mg, 0.404 mmol, 1.5 equiv.)

Linker precursorsHATP*6HCl (141.3 mg, 0.263 mmol, 1 equiv.)

SolventsDI water (20.0 mL for linker solution; 30.0 mL for nickel solution); wash solvents DI water, ethanol, acetone

AdditivesNH4OH (1.50 mL, 21.8 mmol, 83 equiv.)

AtmosphereAir bubbling for 45 min followed by nitrogen bubbling for 2 h; dried under nitrogen.

Temperature65

Time0.75 h air bubbling + 2 h nitrogen bubbling + 15 h drying

Oxidant / reductantAir/oxygen implicated as catalyst; absence of air gave brown solid in yellow solution.

Work-upCentrifuged and decanted; washed with DI water (3 x 40 mL), ethanol (3 x 40 mL), and acetone (2 x 40 mL) with centrifugation and decanting after each wash.

ActivationFor adsorption, pores cleared by soaking powders in water at 100 C (3 x 12 h), then ethanol at 78 C (3 x 12 h), followed by dynamic vacuum to 50 umHg, ramp 2 C/min, hold at 60 C until calibrated, then 100 C for 6 h.

Scalability contextBatch used 0.263 mmol linker and yielded 75.3 mg clumpy black powder.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	*HATP6HCl**	141.3 mg, 0.263 mmol, 1 equiv.	p002-p003 · Syntheses; Porosity method
Metal Source	*NiCl26H2O**	95.7 mg, 0.404 mmol, 1.5 equiv.	p002-p003 · Syntheses; Porosity method
Solvent	DI water	20.0 mL + 30.0 mL	p002-p003 · Syntheses; Porosity method
Base	NH4OH	1.50 mL, 21.8 mmol, 83 equiv.	p002-p003 · Syntheses; Porosity method
Oxidant	air	bubbled 45 min	p002-p003 · Syntheses; Porosity method
Other	nitrogen	bubbled 2 h; drying atmosphere 15 h	p002-p003 · Syntheses; Porosity method