Synthesis · Tunable Charge Transport and Spin Dynamics in Two-Dimensional Conjugated Metal-Organic Frameworks

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: Other

p007 · Ni3(HATI-X)2 synthesis · Figure 1a

Metal precursorsNi(OAc)2.4H2O (1.5 eq)

Linker precursorsHATI_H.6HCl, 5 mg (1 eq), prepared by Boc protection, C-N coupling and acid deprotection in SI Section S2

SolventsDMSO/H2O total 4 mL, typically DMSO:H2O = 3:2 for non-iPr samples, plus 1 mL DMSO linker solution

AdditivesNH4OAc (150 eq); sodium acetate described in main text as a weak base for reducing deprotonation and coordination rate

AtmosphereOpen 10 mL glass vial with stirring; no inert atmosphere reported for final MOF synthesis

Temperature65

Time2

Oxidant / reductantRedox coordination reaction; Ni2+ connects HATI ligand and generates organic radicals

Work-upBlack powder filtered, washed with a large amount of water, DMF and acetone, and dried under vacuum at room temperature

ActivationNo post-synthesis activation beyond vacuum drying; measurement-specific activation used 90 C overnight for sorption/TGA and 150 C vacuum for conductivity/EPR

Scalability contextSmall-scale recipe uses 5 mg linker in an open vial; no scale-up data reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	1.5 eq	p007 · Ni3(HATI-X)2 synthesis · Figure 1a
Linker	HATI_H.6HCl	5 mg, 1 eq · in 1 mL DMSO	p007 · Ni3(HATI-X)2 synthesis · Figure 1a
Additive	NH4OAc	150 eq	p007 · Ni3(HATI-X)2 synthesis · Figure 1a
Solvent	DMSO/H2O	total 4 mL plus 1 mL DMSO · DMSO:H2O typically 3:2	p007 · Ni3(HATI-X)2 synthesis · Figure 1a

Complete recipeSource: Both

Route 2: Other

p007 · Ni3(HATI-X)2 synthesis · Figure 1a

Metal precursorsNi(OAc)2.4H2O (1.5 eq)

Linker precursorsHATI_iPr.6HCl, 5 mg (1 eq), prepared from i-C3H7Br substituted precursor through nucleophilic substitution, C-N coupling and deprotection

SolventsDMSO/H2O total 4 mL, typically DMSO:H2O = 2.5:2.5, plus 1 mL DMSO linker solution

AdditivesNH4OAc (150 eq); sodium acetate described in main text as a weak base

AtmosphereOpen 10 mL glass vial with stirring; no inert atmosphere reported for final MOF synthesis

Temperature65

Time2

Oxidant / reductantRedox coordination reaction; Ni2+ connects HATI ligand and generates organic radicals

Work-upBlack powder filtered, washed with a large amount of water, DMF and acetone, and dried under vacuum at room temperature

ActivationNo post-synthesis activation beyond vacuum drying; measurement-specific activation used 90 C overnight for sorption/TGA and 150 C vacuum for conductivity/EPR

Scalability contextSmall-scale recipe uses 5 mg linker in an open vial; no scale-up data reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	1.5 eq	p007 · Ni3(HATI-X)2 synthesis · Figure 1a
Linker	HATI_iPr.6HCl	5 mg, 1 eq · in 1 mL DMSO	p007 · Ni3(HATI-X)2 synthesis · Figure 1a
Additive	NH4OAc	150 eq	p007 · Ni3(HATI-X)2 synthesis · Figure 1a
Solvent	DMSO/H2O	total 4 mL plus 1 mL DMSO · DMSO:H2O typically 2.5:2.5	p007 · Ni3(HATI-X)2 synthesis · Figure 1a

Complete recipeSource: Both

Route 3: Other

p006-p007 · Section S2 Synthetic procedures · Figure 1a

Metal precursorsNi(OAc)2.4H2O (1.5 eq)

Linker precursorsHATI_nPr.6HCl, 5 mg (1 eq), prepared from n-C3H7Br substituted precursor through nucleophilic substitution, C-N coupling and deprotection

SolventsDMSO/H2O total 4 mL, typically DMSO:H2O = 3:2, plus 1 mL DMSO linker solution

AdditivesNH4OAc (150 eq); sodium acetate described in main text as a weak base

AtmosphereOpen 10 mL glass vial with stirring; no inert atmosphere reported for final MOF synthesis

Temperature65

Time2

Oxidant / reductantRedox coordination reaction; Ni2+ connects HATI ligand and generates organic radicals

Work-upBlack powder filtered, washed with a large amount of water, DMF and acetone, and dried under vacuum at room temperature

ActivationNo post-synthesis activation beyond vacuum drying; measurement-specific activation used 90 C overnight for sorption/TGA and 150 C vacuum for conductivity/EPR

Scalability contextSmall-scale recipe uses 5 mg linker in an open vial; no scale-up data reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	1.5 eq	p006-p007 · Section S2 Synthetic procedures · Figure 1a
Linker	HATI_nPr.6HCl	5 mg, 1 eq · in 1 mL DMSO	p006-p007 · Section S2 Synthetic procedures · Figure 1a
Additive	NH4OAc	150 eq	p006-p007 · Section S2 Synthetic procedures · Figure 1a
Solvent	DMSO/H2O	total 4 mL plus 1 mL DMSO · DMSO:H2O typically 3:2	p006-p007 · Section S2 Synthetic procedures · Figure 1a

Complete recipeSource: Both

Route 4: Other

p006-p007 · Section S2 Synthetic procedures · Figure 1a

Metal precursorsNi(OAc)2.4H2O (1.5 eq)

Linker precursorsHATI_vPr.6HCl, 5 mg (1 eq), prepared from allyl bromide substituted precursor through nucleophilic substitution, C-N coupling and deprotection

SolventsDMSO/H2O total 4 mL, typically DMSO:H2O = 3:2, plus 1 mL DMSO linker solution

AdditivesNH4OAc (150 eq); sodium acetate described in main text as a weak base

AtmosphereOpen 10 mL glass vial with stirring; no inert atmosphere reported for final MOF synthesis

Temperature65

Time2

Oxidant / reductantRedox coordination reaction; Ni2+ connects HATI ligand and generates organic radicals

Work-upBlack powder filtered, washed with a large amount of water, DMF and acetone, and dried under vacuum at room temperature

ActivationNo post-synthesis activation beyond vacuum drying; measurement-specific activation used 90 C overnight for sorption/TGA and 150 C vacuum for conductivity/EPR

Scalability contextSmall-scale recipe uses 5 mg linker in an open vial; no scale-up data reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	1.5 eq	p006-p007 · Section S2 Synthetic procedures · Figure 1a
Linker	HATI_vPr.6HCl	5 mg, 1 eq · in 1 mL DMSO	p006-p007 · Section S2 Synthetic procedures · Figure 1a
Additive	NH4OAc	150 eq	p006-p007 · Section S2 Synthetic procedures · Figure 1a
Solvent	DMSO/H2O	total 4 mL plus 1 mL DMSO · DMSO:H2O typically 3:2	p006-p007 · Section S2 Synthetic procedures · Figure 1a