Synthesis · Dimensionality Modulates Electrical Conductivity in Compositionally Constant One-, Two-, and Three-Dimensional Frameworks

8 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

SI p.10 · Acid/base treatment of Ni-1D

Metal precursorsPreformed Ni-1D

Solvents4 M HCl(aq.) or 1 M KOH methanol solution

AdditivesHCl or KOH

AtmosphereAmbient

Temperatureroom temperature; final drying at 85 C

Time24 h soak; overnight final drying

Oxidant / reductantAcid treatment described as similar to p-doping of polyaniline in main text

Work-upCollected by filtration; washed with water and methanol; dried under air flow.

ActivationDried under vacuum at 85 C overnight.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-1D	Not specified	SI p.10 · Acid/base treatment of Ni-1D
Acid	HCl aqueous solution	4 M	SI p.10 · Acid/base treatment of Ni-1D
Base	KOH methanol solution	1 M	SI p.10 · Acid/base treatment of Ni-1D

Complete recipeSource: Both

Route 2: Solvothermal

SI p.9 · Synthesis of Ni-1D rods/bricks · Figure S12

Metal precursorsNi(OAc)2.4H2O

Linker precursorsTABQ; also obtainable from TAHQ.4HCl under same synthetic procedure

SolventsDI water; concentrated aqueous ammonia solution

AdditivesAqueous ammonia base

AtmosphereAmbient/air inside sealed pressure tube

Temperature120

Time48

Oxidant / reductantAir/ambient conditions promote oxidised water-free Ni-1D formation

Work-upCooled to room temperature; filtered under ambient conditions; washed with large amount of DI water and methanol.

ActivationDried at room temperature under dynamic vacuum for at least 24 h.

Scalability contextMilligram pressure-tube batch.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TABQ	20 mg	SI p.9 · Synthesis of Ni-1D rods/bricks · Figure S12
Metal Source	Ni(OAc)2.4H2O	44 mg	SI p.9 · Synthesis of Ni-1D rods/bricks · Figure S12
Solvent	DI water	0.5 mL	SI p.9 · Synthesis of Ni-1D rods/bricks · Figure S12
Base	concentrated aqueous ammonia solution	2.4 mL · ~14 M	SI p.9 · Synthesis of Ni-1D rods/bricks · Figure S12

Complete recipeSource: SI

Route 3: Solvothermal

SI p.9 · Synthesis of NiTIBQ(D2O/H2O) rods

Metal precursorsNi(OAc)2.4H2O

Linker precursorsTABQ

SolventsDegassed D2O; degassed concentrated aqueous ammonia solution

AdditivesAqueous ammonia base

AtmosphereN2 purging box; sealed pressure tube; filtration under N2

Temperature120

Time48

Work-upCooled to room temperature, filtered under N2, washed with degassed D2O, briefly dried under N2 flow.

ActivationUsed immediately for ATR-FTIR and PXRD.

Scalability contextIsotope labelling batch.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TABQ	20 mg	SI p.9 · Synthesis of NiTIBQ(D2O/H2O) rods
Metal Source	Ni(OAc)2.4H2O	44 mg	SI p.9 · Synthesis of NiTIBQ(D2O/H2O) rods
Solvent	degassed D2O	0.5 mL	SI p.9 · Synthesis of NiTIBQ(D2O/H2O) rods
Base	degassed concentrated aqueous ammonia solution	2.4 mL · ~14 M	SI p.9 · Synthesis of NiTIBQ(D2O/H2O) rods

Complete recipeSource: Both

Route 4: Solvothermal

SI p.9 · Synthesis of Ni-2D rods

Metal precursorsNi(OAc)2.4H2O

Linker precursorsTABQ

SolventsDegassed DI water; degassed concentrated aqueous ammonia solution

AdditivesAqueous ammonia base

AtmosphereN2 purging box; sealed pressure tube; filtration under N2

Temperature120

Time48

Oxidant / reductantInert conditions preserve bridging-water 2D framework formation

Work-upCooled to room temperature, filtered under N2, washed with large amount of degassed DI water, briefly dried under N2 flow.

ActivationUsed immediately; no activation before characterisation.

Scalability context15 mL thick-wall pressure tube, milligram batch.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TABQ	20 mg	SI p.9 · Synthesis of Ni-2D rods
Metal Source	Ni(OAc)2.4H2O	44 mg	SI p.9 · Synthesis of Ni-2D rods
Solvent	degassed DI water	0.5 mL	SI p.9 · Synthesis of Ni-2D rods
Base	degassed concentrated aqueous ammonia solution	2.4 mL · ~14 M	SI p.9 · Synthesis of Ni-2D rods

Complete recipeSource: SI

Route 5: Solvothermal

SI p.10 · Workup in the ambient condition gives Ni-3D-ox · Figure S20

Metal precursorsNi(OAc)2.4H2O

Linker precursorsTAHQ.4HCl

SolventsDegassed concentrated aqueous ammonia solution; DI water workup

AdditivesAqueous ammonia base

AtmosphereInitial N2 synthesis followed by ambient air workup/oxidation

Temperature120

Time24

Oxidant / reductantAir oxidises Ni-3D to Ni-3D-ox

Work-upAfter cooling, filtered and washed with a large amount of DI water under ambient conditions.

ActivationDried under air flow on filtration setup; separate activation at 100-110 C under dynamic vacuum for porosity.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TAHQ.4HCl	15 mg	SI p.10 · Workup in the ambient condition gives Ni-3D-ox · Figure S20
Metal Source	Ni(OAc)2.4H2O	18 mg	SI p.10 · Workup in the ambient condition gives Ni-3D-ox · Figure S20
Base	degassed concentrated aqueous ammonia solution	1 mL · ~14 M	SI p.10 · Workup in the ambient condition gives Ni-3D-ox · Figure S20
Oxidant	air	ambient workup	SI p.10 · Workup in the ambient condition gives Ni-3D-ox · Figure S20

Complete recipeSource: Both

Route 6: Solvothermal

SI p.10 · Synthesis of Ni-3D rods

Metal precursorsNi(OAc)2.4H2O

Linker precursorsTAHQ.4HCl

SolventsDegassed concentrated aqueous ammonia solution

AdditivesAqueous ammonia base

AtmosphereN2 purging box; N2 glove-box workup

Temperature120

Time24

Oxidant / reductantInert conditions preserve reduced brown Ni-3D

Work-upCooled, transferred into N2 glove box, supernatant decanted, brown crystals washed with degassed DI water at least three times.

ActivationDried under N2 flow.

Scalability context15 mL thick-wall pressure-tube batch.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TAHQ.4HCl	15 mg	SI p.10 · Synthesis of Ni-3D rods
Metal Source	Ni(OAc)2.4H2O	18 mg	SI p.10 · Synthesis of Ni-3D rods
Base	degassed concentrated aqueous ammonia solution	1 mL · ~14 M	SI p.10 · Synthesis of Ni-3D rods

Complete recipeSource: SI

Route 7: Other

SI p.8 · Tetraamino-p-benzoquinone (TABQ)

Linker precursorsTetrachloro-p-benzoquinone -> TPBQ -> TABQ

SolventsAcetonitrile; DMF; DMF/EtOH; hydrazine hydrate

AdditivesPotassium phthalimide

AtmosphereN2 for TPBQ reflux; not specified for TABQ deprotection

Temperature80 C for 12 h; 100 C for 30 min; 65 C for 2 h

Time12 h; 0.5 h; 2 h

Oxidant / reductantHydrazine hydrate used to release TABQ from TPBQ

Work-upFiltration, washing with acetonitrile, hot DMF filtration, sonication in DMF/EtOH, then filtration; TABQ washed with DI water until colourless filtrate.

Scalability contextTABQ prepared on gram scale: 3.77 g, 44% yield from 35 g TPBQ.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	tetrachloro-p-benzoquinone	25 g	SI p.8 · Tetraamino-p-benzoquinone (TABQ)
Additive	potassium phthalimide	75 g	SI p.8 · Tetraamino-p-benzoquinone (TABQ)
Solvent	acetonitrile	250 mL	SI p.8 · Tetraamino-p-benzoquinone (TABQ)
Solvent	DMF	100 mL	SI p.8 · Tetraamino-p-benzoquinone (TABQ)
Solvent	DMF/EtOH	v/v = 1:1	SI p.8 · Tetraamino-p-benzoquinone (TABQ)
Reductant	hydrazine hydrate	125 mL · 80.0 wt%	SI p.8 · Tetraamino-p-benzoquinone (TABQ)

Complete recipeSource: SI

Route 8: Other

SI p.9 · Tetraamino-p-hydroquinone tetrahydrochloride (TAHQ.4HCl)

Linker precursorsTABQ -> TAHQ.4HCl

SolventsConcentrated hydrochloric acid; degassed anhydrous methanol wash

AtmosphereN2 atmosphere; filtration in nitrogen-purging box; storage in glove box

Temperatureroom temperature

Time3 h

Oxidant / reductantSnCl2.2H2O reductant

Work-upVacuum filtration in nitrogen-purging box; washed twice with degassed anhydrous methanol; collected and transferred into glove box for drying/storage.

Scalability context1.24 g grey solid, 80% yield.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TABQ (very fine powdered)	825 mg	SI p.9 · Tetraamino-p-hydroquinone tetrahydrochloride (TAHQ.4HCl)
Reductant	SnCl2.2H2O	1.68 g · 1.5-fold excess	SI p.9 · Tetraamino-p-hydroquinone tetrahydrochloride (TAHQ.4HCl)
Acid	concentrated hydrochloric acid	10 mL	SI p.9 · Tetraamino-p-hydroquinone tetrahydrochloride (TAHQ.4HCl)