Synthesis · Nanoporous synthetic metal: A nickel MOF with an amino-functionalized macrocyclic ligand

14 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

S28 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Metal precursorsCu(NO3)2.2.5H2O (7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additives150 uL 2 M aqueous NaOAc (15 equiv.)

Atmospheredegassed N2 bubbled 30 min and capped, or air without bubbling/capping

Temperatureroom temperature

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S28 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Metal Source	Cu(NO3)2.2.5H2O	7 mg, 0.03 mmol	S28 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Base	150 uL 2 M aqueous NaOAc (15 equiv.)	varied or 150 uL · 2 M aqueous	S28 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Complete recipeSource: SI

Route 2: Other

S26 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Metal precursorsCu(NO3)2.2.5H2O (7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additivesaqueous NaOAc 2 M, 12-18 equiv.

Atmospherewithout capping

Temperatureroom temperature

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S26 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Metal Source	Cu(NO3)2.2.5H2O	7 mg, 0.03 mmol	S26 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Base	aqueous NaOAc 2 M, 12-18 equiv.	varied or 150 uL · 2 M aqueous	S26 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Complete recipeSource: SI

Route 3: Other

S29 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Metal precursorsCu(NO3)2.2.5H2O (7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

Solvents10-20 mL total DMSO/water (1:1, v/v)

Additives150 uL 2 M aqueous NaOAc (15 equiv.)

Atmospherewithout capping

Temperatureroom temperature

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S29 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Metal Source	Cu(NO3)2.2.5H2O	7 mg, 0.03 mmol	S29 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Base	150 uL 2 M aqueous NaOAc (15 equiv.)	varied or 150 uL · 2 M aqueous	S29 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Complete recipeSource: Both

Route 4: Other

p. 6 · Methods - Synthesis of Cu-HATC

Metal precursorsCu(NO3)2.2.5H2O (7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (7.5 mL) and water (7.5 mL) in main optimal route; SI optimisations also use 5/5 mL and 10-20 mL total

Additives150 uL of 2 M aqueous NaOAc (15 equiv.)

Atmosphereair/open; without capping for optimal route

Temperatureroom temperature

Time16

Oxidant / reductantnone specified

Work-upcentrifuge black solids; wash DMF (2 x 10 mL), acetone (2 x 10 mL)

Activationvacuum oven at 70 C, 20 mTorr, 1 h

Scalability contextmain route uses 15 mL total solvent; SI concentration screen covers 10-20 mL total solvent.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	p. 6 · Methods - Synthesis of Cu-HATC
Metal Source	Cu(NO3)2.2.5H2O	7 mg, 0.03 mmol	p. 6 · Methods - Synthesis of Cu-HATC
Solvent	DMSO	7.5 mL	p. 6 · Methods - Synthesis of Cu-HATC
Solvent	water	7.5 mL	p. 6 · Methods - Synthesis of Cu-HATC
Base	NaOAc	150 uL · 2 M aqueous	p. 6 · Methods - Synthesis of Cu-HATC

Complete recipeSource: SI

Route 5: Other

S27 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Metal precursorsCu(NO3)2.2.5H2O (7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additives150 uL 2 M aqueous NaOAc (15 equiv.)

Atmospherewithout capping

Temperatureroom temperature to 40

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S27 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Metal Source	Cu(NO3)2.2.5H2O	7 mg, 0.03 mmol	S27 · Synthesis and characterization of Cu-HATC · Figures S32-S35
Base	150 uL 2 M aqueous NaOAc (15 equiv.)	varied or 150 uL · 2 M aqueous	S27 · Synthesis and characterization of Cu-HATC · Figures S32-S35

Complete recipeSource: Both

Route 6: Solvothermal

S34 · Synthesis and characterization of Cu-HHTC

Metal precursorsCu(NO3)2.2.5H2O (11.7 mg, 0.05 mmol)

Linker precursorsHHTC ligand (10 mg, 0.025 mmol)

Solventsdegassed DMF (5 mL) and degassed water (5 mL)

Additivesnone reported

Atmospheredegassed solvents; stirred in vial

Temperature50

Time8 h in SI; 12 h in main methods

Oxidant / reductantnone specified

Work-upcool to room temperature; centrifuge black solids; wash DMF (2 x 10 mL), acetone (2 x 10 mL)

Activationvacuum oven at 70 C, 20 mTorr, 1 h

Scalability contextReported-method analog synthesis; source time differs between main and SI.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTC ligand	10 mg, 0.025 mmol	S34 · Synthesis and characterization of Cu-HHTC
Metal Source	Cu(NO3)2.2.5H2O	11.7 mg, 0.05 mmol	S34 · Synthesis and characterization of Cu-HHTC
Solvent	degassed DMF	5 mL	S34 · Synthesis and characterization of Cu-HHTC
Solvent	degassed H2O	5 mL	S34 · Synthesis and characterization of Cu-HHTC

Complete recipeSource: Both

Route 7: Solvothermal

p. 6 · Methods - Synthesis of bulk powder Ni-HATC

Metal precursorsNi(NO3)2.6H2O (8.7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additives150 uL of 2 M aqueous sodium acetate (NaOAc), 15 equiv.

Atmospherenot specified; reaction vial, no degassing reported for optimal Ni-HATC

Temperature80

Time16

Oxidant / reductantnone specified

Work-upcool to room temperature; centrifuge black solids; wash DMF (2 x 10 mL), acetone (2 x 10 mL)

Activationvacuum oven at 70 C, 20 mTorr, 1 h

Scalability context0.02 mmol ligand batch in 20 mL vial; optimisation shows sensitivity to base, temperature, solvent ratio, concentration and time.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	p. 6 · Methods - Synthesis of bulk powder Ni-HATC
Metal Source	Ni(NO3)2.6H2O	8.7 mg, 0.03 mmol	p. 6 · Methods - Synthesis of bulk powder Ni-HATC
Solvent	DMSO	5 mL	p. 6 · Methods - Synthesis of bulk powder Ni-HATC
Solvent	water	5 mL	p. 6 · Methods - Synthesis of bulk powder Ni-HATC
Base	aqueous sodium acetate (NaOAc)	150 uL · 2 M	p. 6 · Methods - Synthesis of bulk powder Ni-HATC

Complete recipeSource: SI

Route 8: Solvothermal

S19 · Synthetic optimization of Ni-HATC · Figures S17-S22

Metal precursorsNi(NO3)2.6H2O (8.7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

Solvents5-15 mL total DMSO/water (1:1, v/v)

Additives150 uL 2 M aqueous NaOAc (15 equiv.)

Atmospherenot specified

Temperature80

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S19 · Synthetic optimization of Ni-HATC · Figures S17-S22
Metal Source	Ni(NO3)2.6H2O	8.7 mg, 0.03 mmol	S19 · Synthetic optimization of Ni-HATC · Figures S17-S22
Base	150 uL 2 M aqueous NaOAc (15 equiv.)	varied as stated · 2 M aqueous	S19 · Synthetic optimization of Ni-HATC · Figures S17-S22

Complete recipeSource: SI

Route 9: Solvothermal

S16 · Synthetic optimization of Ni-HATC · Figures S17-S22

Metal precursorsNi(NO3)2.6H2O (8.7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additives2 M aqueous NaOAc, 9-18 equiv.

Atmospherenot specified

Temperature80

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S16 · Synthetic optimization of Ni-HATC · Figures S17-S22
Metal Source	Ni(NO3)2.6H2O	8.7 mg, 0.03 mmol	S16 · Synthetic optimization of Ni-HATC · Figures S17-S22
Base	2 M aqueous NaOAc, 9-18 equiv.	varied as stated · 2 M aqueous	S16 · Synthetic optimization of Ni-HATC · Figures S17-S22

Complete recipeSource: SI

Route 10: Solvothermal

S15 · Synthetic optimization of Ni-HATC · Figures S17-S22

Metal precursorsNi(NO3)2.6H2O (8.7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additives2 M aqueous NH4OH, 12-75 equiv.

Atmospherenot specified

Temperature80

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S15 · Synthetic optimization of Ni-HATC · Figures S17-S22
Metal Source	Ni(NO3)2.6H2O	8.7 mg, 0.03 mmol	S15 · Synthetic optimization of Ni-HATC · Figures S17-S22
Base	2 M aqueous NH4OH, 12-75 equiv.	varied as stated · 2 M aqueous	S15 · Synthetic optimization of Ni-HATC · Figures S17-S22

Complete recipeSource: SI

Route 11: Solvothermal

S18 · Synthetic optimization of Ni-HATC · Figures S17-S22

Metal precursorsNi(NO3)2.6H2O (8.7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

Solvents10 mL total DMSO/water, ratios 3/7, 5/5, 7/3

Additives150 uL 2 M aqueous NaOAc (15 equiv.)

Atmospherenot specified

Temperature80

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S18 · Synthetic optimization of Ni-HATC · Figures S17-S22
Metal Source	Ni(NO3)2.6H2O	8.7 mg, 0.03 mmol	S18 · Synthetic optimization of Ni-HATC · Figures S17-S22
Base	150 uL 2 M aqueous NaOAc (15 equiv.)	varied as stated · 2 M aqueous	S18 · Synthetic optimization of Ni-HATC · Figures S17-S22

Complete recipeSource: SI

Route 12: Solvothermal

S17 · Synthetic optimization of Ni-HATC · Figures S17-S22

Metal precursorsNi(NO3)2.6H2O (8.7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additives150 uL 2 M aqueous NaOAc (15 equiv.)

Atmospherenot specified

Temperature60-90

Time16

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S17 · Synthetic optimization of Ni-HATC · Figures S17-S22
Metal Source	Ni(NO3)2.6H2O	8.7 mg, 0.03 mmol	S17 · Synthetic optimization of Ni-HATC · Figures S17-S22
Base	150 uL 2 M aqueous NaOAc (15 equiv.)	varied as stated · 2 M aqueous	S17 · Synthetic optimization of Ni-HATC · Figures S17-S22

Complete recipeSource: Main

Route 13: Solvothermal

p. 6 · Methods - Synthesis of thin film Ni-HATC

Metal precursorssame components as solvothermal Ni-HATC synthesis: Ni(NO3)2.6H2O

Linker precursorssame components as solvothermal Ni-HATC synthesis: HATC.6HCl

Solventssame Ni-HATC reaction solution: DMSO/water with NaOAc

AdditivesNaOAc as in bulk synthesis

Atmospherenot specified

Temperature80 inferred from same solvothermal synthesis

Time16 inferred from same solvothermal synthesis

Substrate orientationcleaned glass slide, 20 mm x 15 mm x 1 mm, placed in reaction vial

Oxidant / reductantnone specified

Work-upsoak film in DMF (2 x 10 mL), then acetone (2 x 10 mL)

Activationvacuum oven at 70 C, 20 mTorr, 1 h

Scalability contextthin film area approximately 20 mm x 15 mm; inset reports ~15 mm coverage width

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	same as bulk Ni-HATC synthesis	p. 6 · Methods - Synthesis of thin film Ni-HATC
Metal Source	Ni(NO3)2.6H2O	same as bulk Ni-HATC synthesis	p. 6 · Methods - Synthesis of thin film Ni-HATC
Base	NaOAc	same as bulk Ni-HATC synthesis · 2 M aqueous	p. 6 · Methods - Synthesis of thin film Ni-HATC
Other	glass slide	20 mm x 15 mm x 1 mm	p. 6 · Methods - Synthesis of thin film Ni-HATC

Complete recipeSource: SI

Route 14: Solvothermal

S20 · Synthetic optimization of Ni-HATC · Figures S17-S22

Metal precursorsNi(NO3)2.6H2O (8.7 mg, 0.03 mmol)

Linker precursorsHATC.6HCl (12.2 mg, 0.02 mmol)

SolventsDMSO (5 mL) and water (5 mL)

Additives150 uL 2 M aqueous NaOAc (15 equiv.)

Atmospherenot specified

Temperature80

Time12-20

Oxidant / reductantnone specified

Work-upcentrifugation; wash DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activation70 C oven under reduced pressure for further characterization

Scalability contextoptimisation experiment, not necessarily best-performing sample

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATC.6HCl	12.2 mg, 0.02 mmol	S20 · Synthetic optimization of Ni-HATC · Figures S17-S22
Metal Source	Ni(NO3)2.6H2O	8.7 mg, 0.03 mmol	S20 · Synthetic optimization of Ni-HATC · Figures S17-S22
Base	150 uL 2 M aqueous NaOAc (15 equiv.)	varied as stated · 2 M aqueous	S20 · Synthetic optimization of Ni-HATC · Figures S17-S22