Synthesis · Superior Charge Transport in Ni-Diamine Conductive MOFs

Complete recipeSource: Both

Route 1: Other

8 · Cu3(HITT)2 synthesis

Metal precursorsCuCl

Linker precursorsHATT.3HCl

SolventsDMF and H2O; linker dissolved in degassed DMF/degassed H2O; metal source in DMF

Additivesaqueous sodium acetate

Atmosphereopen vial; degassed DMF/H2O used for linker solution

Temperature25

Time3

Oxidant / reductantCu+ precursor; ambient air can later oxidise product during exposure studies

Work-upcentrifuged, decanted, washed twice with deionised water and twice with acetone

Activationdried under vacuum at room temperature; porosity sample degassed at 55 deg C overnight before N2 measurement

Scalability contextSmall-vial batch: 20.7 mg HATT.3HCl and 0.06 mmol CuCl; no scale-up reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuCl	6 mL; 0.06 mmol · 10 mM in DMF	8 · Cu3(HITT)2 synthesis
Linker	HATT•3HCl	20.7 mg; 0.04 mmol · dissolved in 4 mL degassed DMF and 1 mL degassed H2O	8 · Cu3(HITT)2 synthesis
Base	aqueous sodium acetate	1 mL · 4 M	8 · Cu3(HITT)2 synthesis
Solvent	DMF	6 mL metal solution + 4 mL linker solution · degassed for linker solution	8 · Cu3(HITT)2 synthesis
Solvent	H2O	1 mL linker solution · degassed	8 · Cu3(HITT)2 synthesis

Complete recipeSource: SI

Route 2: Other

6-8 · Ligand synthesis procedure · Figures S2-S10

Linker precursors3,4-dibromobenzaldehyde via intermediates 2, 3, 4 and 5

Solventsdiethyl ether; cyclohexane/benzene; EtOAc/MeOH; sulfolane/acetic acid; dry toluene; DCM/acetone; THF; n-hexane

Additivesred fuming HNO3, concentrated H2SO4, SnCl2, ammonium acetate, Pd2(dba)3, rac-BINAP, sodium tert-butoxide, benzophenone imine, concentrated HCl

AtmosphereIce bath for nitration and acid deprotection; N2 bubbling/Schlenk conditions for Buchwald amination and HCl deprotection steps.

Temperaturemultistep: ice bath/RT; 70; 180; 115; 0; 40-80 drying

Timemultistep: 1 h addition + 1 h; 24 h; 4 days; 16 h; 2 h

Oxidant / reductantHNO3/H2SO4 nitration; SnCl2 reduction; Pd-catalysed amination; HCl deprotection

Work-upWashing, decanting, recrystallisation, extraction, Celite filtration, column chromatography, centrifugation and sequential THF/n-hexane washes as described for intermediates 2-6.

ActivationFinal HATT.3HCl dried at 60 deg C under vacuum; intermediates dried under reduced pressure/vacuum as specified.

Scalability contextLigand route reported from 10 g 3,4-dibromobenzaldehyde to 1.2 g final HATT.3HCl; no scale-up beyond this batch reported.

Show 15 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	3,4-dibromobenzaldehyde	10 g	6-8 · Ligand synthesis procedure · Figures S2-S10
Acid	red fuming HNO3	10 mL	6-8 · Ligand synthesis procedure · Figures S2-S10
Acid	concentrated H2SO4	6 mL	6-8 · Ligand synthesis procedure · Figures S2-S10
Reductant	SnCl2	23.7 g; 125.1 mmol	6-8 · Ligand synthesis procedure · Figures S2-S10
Solvent	EtOAc:MeOH	270 mL · 1:1	6-8 · Ligand synthesis procedure · Figures S2-S10
Additive	ammonium acetate	2.16 g; 28 mmol	6-8 · Ligand synthesis procedure · Figures S2-S10
Solvent	sulfolane	25 mL	6-8 · Ligand synthesis procedure · Figures S2-S10
Solvent	glacial acetic acid	6 mL	6-8 · Ligand synthesis procedure · Figures S2-S10
Additive	Pd2(dba)3	330 mg; 0.36 mmol	6-8 · Ligand synthesis procedure · Figures S2-S10
Additive	rac-BINAP	448.3 mg; 0.72 mmol	6-8 · Ligand synthesis procedure · Figures S2-S10
Base	sodium tert-butoxide	2.25 g; 23.4 mmol	6-8 · Ligand synthesis procedure · Figures S2-S10
Other	benzophenone imine	3.94 mL; 23.4 mmol	6-8 · Ligand synthesis procedure · Figures S2-S10
Solvent	dry toluene	150 mL	6-8 · Ligand synthesis procedure · Figures S2-S10
Acid	concentrated hydrochloric acid	75 mL · bubbled with N2 before use	6-8 · Ligand synthesis procedure · Figures S2-S10
Solvent	tetrahydrofuran	100 mL	6-8 · Ligand synthesis procedure · Figures S2-S10

Complete recipeSource: Both

Route 3: Other

8 · Ni3(HITT)2 synthesis

Metal precursorsNi(NO3)2.6H2O

Linker precursorsHATT.3HCl

SolventsDMF and H2O; linker dissolved in degassed DMF/degassed H2O; metal source in DMF

Additivesaqueous sodium acetate

Atmosphereopen vial in air; degassed DMF/H2O used for linker solution

Temperature45

Time3

Oxidant / reductantair deprotonates/oxidises HATT according to main text; no separate oxidant added

Work-upcentrifuged, decanted, washed twice with deionised water and twice with acetone

Activationdried under vacuum at room temperature; porosity sample degassed at 120 deg C overnight before N2 measurement

Scalability contextSmall-vial batch: 20.7 mg HATT.3HCl and 0.06 mmol metal salt; no scale-up reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2•6H2O	6 mL; 0.06 mmol · 10 mM in DMF	8 · Ni3(HITT)2 synthesis
Linker	HATT•3HCl	20.7 mg; 0.04 mmol · dissolved in 4 mL degassed DMF and 1 mL degassed H2O	8 · Ni3(HITT)2 synthesis
Base	aqueous sodium acetate	1 mL · 4 M	8 · Ni3(HITT)2 synthesis
Solvent	DMF	6 mL metal solution + 4 mL linker solution · degassed for linker solution	8 · Ni3(HITT)2 synthesis
Solvent	H2O	1 mL linker solution · degassed	8 · Ni3(HITT)2 synthesis

Superior Charge Transport in Ni-Diamine Conductive MOFs

3 structured synthesis routes