Synthesis · Continuous Electrical Conductivity Variation in M3(Hexaiminotriphenylene)2(M = Co, Ni, Cu) MOF Alloys

22 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

S8 · Section S2 · blend procedures

Metal precursorspreformed Co3(HITP)2 and Cu3(HITP)2 powders

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

Solventsnone

Additivesnone

Atmosphereambient

Oxidant / reductantnone

Work-uppestle-and-mortar blending

Activationnone

Scalability contextSmall-vial synthesis at 5 mg HATP.6HCl screening scale; no scale-up demonstrated.

Complete recipeSource: SI

Route 2: Other

S8 · Section S2 · blend procedures

Metal precursorspreformed Co3(HITP)2 and Ni3(HITP)2 powders

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

Solventsnone

Additivesnone

Atmosphereambient

Oxidant / reductantnone

Work-uppestle-and-mortar blending

Activationnone

Scalability contextSmall-vial synthesis at 5 mg HATP.6HCl screening scale; no scale-up demonstrated.

Complete recipeSource: SI

Route 3: Other

S7-S12 · Section S2/S3 · Co3(HITP)2 particles; Figure S2

Metal precursorscobalt(II) nitrate hexahydrate (Co(NO3)2.6H2O), 1.5 mL stock, 62.1 mmol/L, 10 eq.

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF; water

AdditivesNaOAc aqueous solution, 2 mL, 2 mol/L

Atmosphereopen glass vial; air present unless noted

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationporosity samples activated at 90 C under high dynamic vacuum for 24 h before N2 sorption

Scalability contextSmall-vial synthesis at 5 mg HATP.6HCl screening scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	cobalt(II) nitrate hexahydrate (Co(NO3)2.6H2O)	1.5 mL stock solution; 10 eq. · 62.1 mmol L-1	S7-S12 · Section S2/S3 · Co3(HITP)2 particles; Figure S2
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S7-S12 · Section S2/S3 · Co3(HITP)2 particles; Figure S2
Solvent	DMF	1.5 mL metal stock solvent	S7-S12 · Section S2/S3 · Co3(HITP)2 particles; Figure S2
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S7-S12 · Section S2/S3 · Co3(HITP)2 particles; Figure S2

Complete recipeSource: SI

Route 4: Other

S8 · Section S2 · cocu alloy synthesis

Metal precursorsCo(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF plus 1 mL DMA; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution plus 1 mL DMA · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cocu alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cocu alloy synthesis
Solvent	DMF plus 1 mL DMA; water	see route solvents and metal stock	S8 · Section S2 · cocu alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · cocu alloy synthesis

Complete recipeSource: SI

Route 5: Other

S8 · Section S2 · cocu alloy synthesis

Metal precursorsCo(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF plus 1 mL DMA; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution plus 1 mL DMA · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cocu alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cocu alloy synthesis
Solvent	DMF plus 1 mL DMA; water	see route solvents and metal stock	S8 · Section S2 · cocu alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · cocu alloy synthesis

Complete recipeSource: SI

Route 6: Other

S8 · Section S2 · cocu alloy synthesis

Metal precursorsCo(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF plus 1 mL DMA; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution plus 1 mL DMA · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cocu alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cocu alloy synthesis
Solvent	DMF plus 1 mL DMA; water	see route solvents and metal stock	S8 · Section S2 · cocu alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · cocu alloy synthesis

Complete recipeSource: SI

Route 7: Other

S8 · Section S2 · cocu alloy synthesis

Metal precursorsCo(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF plus 1 mL DMA; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution plus 1 mL DMA · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cocu alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cocu alloy synthesis
Solvent	DMF plus 1 mL DMA; water	see route solvents and metal stock	S8 · Section S2 · cocu alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · cocu alloy synthesis

Complete recipeSource: SI

Route 8: Other

S8 · Section S2 · cocu alloy synthesis

Metal precursorsCo(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF plus 1 mL DMA; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution plus 1 mL DMA · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cocu alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cocu alloy synthesis
Solvent	DMF plus 1 mL DMA; water	see route solvents and metal stock	S8 · Section S2 · cocu alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · cocu alloy synthesis

Complete recipeSource: SI

Route 9: Other

S8 · Section S2 · cocu alloy synthesis

Metal precursorsCo(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF plus 1 mL DMA; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and CuSO4.5H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3, 4:11 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution plus 1 mL DMA · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cocu alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cocu alloy synthesis
Solvent	DMF plus 1 mL DMA; water	see route solvents and metal stock	S8 · Section S2 · cocu alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · cocu alloy synthesis

Complete recipeSource: SI

Route 10: Other

S8 · Section S2 · coni alloy synthesis

Metal precursorsCo(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · coni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · coni alloy synthesis
Solvent	DMF; water	see route solvents and metal stock	S8 · Section S2 · coni alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · coni alloy synthesis

Complete recipeSource: SI

Route 11: Other

S8 · Section S2 · coni alloy synthesis

Metal precursorsCo(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · coni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · coni alloy synthesis
Solvent	DMF; water	see route solvents and metal stock	S8 · Section S2 · coni alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · coni alloy synthesis

Complete recipeSource: SI

Route 12: Other

S8 · Section S2 · coni alloy synthesis

Metal precursorsCo(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · coni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · coni alloy synthesis
Solvent	DMF; water	see route solvents and metal stock	S8 · Section S2 · coni alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · coni alloy synthesis

Complete recipeSource: SI

Route 13: Other

S8 · Section S2 · coni alloy synthesis

Metal precursorsCo(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · coni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · coni alloy synthesis
Solvent	DMF; water	see route solvents and metal stock	S8 · Section S2 · coni alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · coni alloy synthesis

Complete recipeSource: SI

Route 14: Other

S8 · Section S2 · coni alloy synthesis

Metal precursorsCo(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF; water

Additives2 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 4.66 mmol/L	3 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · coni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · coni alloy synthesis
Solvent	DMF; water	see route solvents and metal stock	S8 · Section S2 · coni alloy synthesis
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S8 · Section S2 · coni alloy synthesis

Complete recipeSource: SI

Route 15: Other

S7-S14 · Section S2/S3 · Cu3(HITP)2 rods; Figure S4

Metal precursorscopper(II) sulfate pentahydrate (CuSO4.5H2O), 3.5 mg, 0.014 mmol, 1.5 eq.

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMA; water

AdditivesNaOAc aqueous solution, 2 mL, 2 mol/L

Atmosphereopen glass vial; air present unless noted

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationporosity samples activated at 90 C under high dynamic vacuum for 24 h before N2 sorption

Scalability contextSmall-vial synthesis at 5 mg HATP.6HCl screening scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper(II) sulfate pentahydrate (CuSO4.5H2O)	3.5 mg (0.014 mmol, 1.5 eq.)	S7-S14 · Section S2/S3 · Cu3(HITP)2 rods; Figure S4
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S7-S14 · Section S2/S3 · Cu3(HITP)2 rods; Figure S4
Solvent	DMA	1.5 mL	S7-S14 · Section S2/S3 · Cu3(HITP)2 rods; Figure S4
Base	NaOAc aqueous solution	2 mL · 2 mol L-1	S7-S14 · Section S2/S3 · Cu3(HITP)2 rods; Figure S4

Complete recipeSource: SI

Route 16: Other

S8 · Section S2 · cuni alloy synthesis

Metal precursorsCuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF/DMA (v/v = 1:1); water

Additives4 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L	6 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cuni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cuni alloy synthesis
Solvent	DMF/DMA (v/v = 1:1); water	see route solvents and metal stock	S8 · Section S2 · cuni alloy synthesis
Base	NaOAc aqueous solution	4 mL · 2 mol L-1	S8 · Section S2 · cuni alloy synthesis

Complete recipeSource: SI

Route 17: Other

S8 · Section S2 · cuni alloy synthesis

Metal precursorsCuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF/DMA (v/v = 1:1); water

Additives4 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L	6 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cuni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cuni alloy synthesis
Solvent	DMF/DMA (v/v = 1:1); water	see route solvents and metal stock	S8 · Section S2 · cuni alloy synthesis
Base	NaOAc aqueous solution	4 mL · 2 mol L-1	S8 · Section S2 · cuni alloy synthesis

Complete recipeSource: SI

Route 18: Other

S8 · Section S2 · cuni alloy synthesis

Metal precursorsCuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF/DMA (v/v = 1:1); water

Additives4 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L	6 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cuni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cuni alloy synthesis
Solvent	DMF/DMA (v/v = 1:1); water	see route solvents and metal stock	S8 · Section S2 · cuni alloy synthesis
Base	NaOAc aqueous solution	4 mL · 2 mol L-1	S8 · Section S2 · cuni alloy synthesis

Complete recipeSource: SI

Route 19: Other

S8 · Section S2 · cuni alloy synthesis

Metal precursorsCuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF/DMA (v/v = 1:1); water

Additives4 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L	6 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cuni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cuni alloy synthesis
Solvent	DMF/DMA (v/v = 1:1); water	see route solvents and metal stock	S8 · Section S2 · cuni alloy synthesis
Base	NaOAc aqueous solution	4 mL · 2 mol L-1	S8 · Section S2 · cuni alloy synthesis

Complete recipeSource: SI

Route 20: Other

S8 · Section S2 · cuni alloy synthesis

Metal precursorsCuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF/DMA (v/v = 1:1); water

Additives4 mL NaOAc aqueous solution (2 mol/L)

Atmosphereopen glass vial; air present

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationnot explicitly stated for alloy powders except N2 samples activated at 90 C before porosity analysis

Scalability contextSmall-vial 5 mg HATP.6HCl scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O and Ni(OAc)2.4H2O mixed salts; precursor mole ratios 4:1, 3:2, 1:1, 2:3 and 1:4; total metal concentration 2.33 mmol/L	6 mL mixed salt stock solution · 2.33 mmol L-1 for Cu/Ni; 4.66 mmol L-1 for Co/Ni or Co/Cu	S8 · Section S2 · cuni alloy synthesis
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S8 · Section S2 · cuni alloy synthesis
Solvent	DMF/DMA (v/v = 1:1); water	see route solvents and metal stock	S8 · Section S2 · cuni alloy synthesis
Base	NaOAc aqueous solution	4 mL · 2 mol L-1	S8 · Section S2 · cuni alloy synthesis

Complete recipeSource: SI

Route 21: Other

S7 · Section S2 · Alternative Ni3(HITP)2 procedure

Metal precursorsnickel(II) acetate tetrahydrate (Ni(OAc)2.4H2O), 6 mL stock, 2.33 mmol/L, 1.5 eq.

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMF/DMA (v/v = 1:1); water

AdditivesNaOAc aqueous solution, 4 mL, 2 mol/L

Atmosphereopen glass vial; air present unless noted

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationporosity samples activated at 90 C under high dynamic vacuum for 24 h before N2 sorption

Scalability contextSmall-vial synthesis at 5 mg HATP.6HCl screening scale; no scale-up demonstrated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	6 mL stock solution; 1.5 eq. · 2.33 mmol L-1	S7 · Section S2 · Alternative Ni3(HITP)2 procedure
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S7 · Section S2 · Alternative Ni3(HITP)2 procedure
Solvent	DMF/DMA	6 mL stock solvent · v/v = 1:1	S7 · Section S2 · Alternative Ni3(HITP)2 procedure
Base	NaOAc aqueous solution	4 mL · 2 mol L-1	S7 · Section S2 · Alternative Ni3(HITP)2 procedure

Complete recipeSource: SI

Route 22: Other

S7 · Section S2 · Ni3(HITP)2 rods

Metal precursorsnickel(II) acetate tetrahydrate (Ni(OAc)2.4H2O), 1.5 mL stock, 9.31 mmol/L, 1.5 eq.

Linker precursorsHATP.6HCl, 5 mg (0.0093 mmol, 1 eq.) in 1.5 mL water

SolventsDMSO; water

AdditivesNaOAc aqueous solution, 2 mL, 4 mol/L

Atmosphereopen glass vial; air present unless noted

Temperature65

Time2

Oxidant / reductantair/partial oxidation by air

Work-upblack powder filtered, washed with large amount of water and methanol, dried under vacuum

Activationporosity samples activated at 90 C under high dynamic vacuum for 24 h before N2 sorption

Scalability contextSmall-vial synthesis at 5 mg HATP.6HCl screening scale; no scale-up demonstrated.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel(II) acetate tetrahydrate (Ni(OAc)2.4H2O)	1.5 mL stock solution; 1.5 eq. · 9.31 mmol L-1	S7 · Section S2 · Ni3(HITP)2 rods
Linker	HATP.6HCl	5 mg (0.0093 mmol, 1 eq.)	S7 · Section S2 · Ni3(HITP)2 rods
Solvent	DMSO	1.5 mL metal stock solvent	S7 · Section S2 · Ni3(HITP)2 rods
Solvent	water	1.5 mL linker solution + aqueous base	S7 · Section S2 · Ni3(HITP)2 rods
Base	NaOAc aqueous solution	2 mL · 4 mol L-1	S7 · Section S2 · Ni3(HITP)2 rods