Synthesis · Controlling the Spatiotemporal Self-Organization of Stimuli-Responsive Nanocrystals under Out-of-Equilibrium Conditions

5 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

3 · S2 Synthetic procedure · Figure S3

Metal precursorsnickel acetate tetrahydrate, 150 mM outer electrolyte

Linker precursorsHATP.6HCl, 10 mM inner electrolyte

SolventsDI water and DMF, 7:3 volume ratio

Additivesbacteriological agar, sodium acetate base (100 molar equivalents with respect to ligand)

Atmosphereambient air; no inert atmosphere reported

Temperature85 for gel/inner electrolyte preparation; room temperature reaction after gelation

Time6 h gelation; 240 h reaction/diffusion; 12 h drying at 60 C; activation solvent exchange 2 days ethanol plus 2 days acetone; final 48 h drying at 62 C

Substrate orientation1D agar gel column in 16 x 180 mm pyrex tube; nickel outer electrolyte poured on top of gel matrix

Oxidant / reductantnone intentionally added

Work-upGel column removed, cut into equidistant zones, washed with hot DI water (40 mL x 6 each), exchanged with DMF (40 mL x 1) and acetone (40 mL x 5), centrifuged and vacuum dried.

ActivationSoaked in ethanol for 2 days with fresh ethanol every 8 h, then acetone exchange by same process, then vacuum dried 48 h at 62 C.

Scalability contextOptimised 1D synthesis gives particle-size libraries in a one-pot reaction-diffusion route but low conversion in larger 1D geometry.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel acetate tetrahydrate	186 mg · 150 mM in 5 mL DI water/DMF	3 · S2 Synthetic procedure · Figure S3
Linker	HATP.6HCl	78 mg · 10 mM in inner electrolyte	3 · S2 Synthetic procedure · Figure S3
Base	sodium acetate	1.2 g · 100 molar equivalents relative to ligand	3 · S2 Synthetic procedure · Figure S3
Additive	bacteriological agar	150 mg · 1% w/w	3 · S2 Synthetic procedure · Figure S3
Solvent	deionized water	8 mL hot DI water for agar; 2.5 mL DI water for NaOAc; 3.5 mL DI water for Ni salt	3 · S2 Synthetic procedure · Figure S3
Solvent	N,N-dimethylformamide (DMF)	4.5 mL for HATP.6HCl; 1.5 mL added to Ni solution	3 · S2 Synthetic procedure · Figure S3

Partial recipeSource: Both

Route 2: Other

1589 · 3.4 2D Liesegang Rings · Figure 4; Figure S70

Metal precursorsnickel acetate / Ni2+ solution, 150 mM

Linker precursorsHATP.6HCl, 10 mM in agar gel film

SolventsDI water and DMF, phi_DMF = 0.3

Additivesagar gel and NaOAc base

Atmosphereambient air; no inert atmosphere reported

Temperature85/80 during gel preparation; room temperature 2D diffusion reaction

Timeabout 7 days to 10 days for 2D Liesegang-ring formation

Substrate orientationthin agar gel film in 10 cm diameter, 1 cm high circular reactor; Ni2+ placed in a groove at the centre and allowed to diffuse radially

Oxidant / reductantnone intentionally added

Work-upFour zones, each containing 2-3 rings, isolated from gel film and activated/washed as in Section S2.

ActivationSame activation as Section S2: ethanol exchange, acetone exchange, vacuum drying.

Scalability context2D reactor increased reaction surface area and overall conversion to more than 54%, compared with 11% for larger 1D reactor.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel acetate / Ni2+	150 mM	1589 · 3.4 2D Liesegang Rings · Figure 4; Figure S70
Linker	HATP.6HCl	10 mM	1589 · 3.4 2D Liesegang Rings · Figure 4; Figure S70
Base	sodium acetate	same as S2 / 100 equivalents relative to ligand	1589 · 3.4 2D Liesegang Rings · Figure 4; Figure S70
Additive	agar	1% w/w	1589 · 3.4 2D Liesegang Rings · Figure 4; Figure S70
Solvent	DI water:DMF	phi_DMF = 0.3	1589 · 3.4 2D Liesegang Rings · Figure 4; Figure S70

Complete recipeSource: SI

Route 3: Solvothermal

91 · S11.8.1 Synthesis procedure and activation

Metal precursorsNi(OAc)2

Linker precursorsHATP.6HCl

SolventsDMF, DMAC and DI water

AdditivesNaOAc

Atmospherenot specified

Temperature65 preheat; 70 reaction; 65 drying/activation

Time0.5 h preheat; 3 h heating at 70 C; two-day washing period; 24 h drying; 2 days ethanol activation plus 2 days acetone activation; 36 h final vacuum drying

Substrate orientation20 mL glass vial solution-phase synthesis

Oxidant / reductantnone intentionally added

Work-upBlack powder centrifuged, washed with DI water (30 mL x3), ethanol (30 mL x1), and acetone (30 mL x3) over two days, then vacuum dried 24 h at 65 C.

ActivationSoaked in 15 mL ethanol for 2 days with solvent exchange every 12 h, followed by acetone for another 2 days; final vacuum oven 65 C for 36 h.

Scalability contextConventional bulk solution-phase control, not the RD patterning approach.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2	3.46 mg · 2.33 mmol L-1, 1.5 eq	91 · S11.8.1 Synthesis procedure and activation
Linker	HATP.6HCl	5 mg · 0.0093 mmol, 1 eq	91 · S11.8.1 Synthesis procedure and activation
Base	NaOAc	4 mL aqueous solution · 8.00 mmol, 860 eq	91 · S11.8.1 Synthesis procedure and activation
Solvent	DMF:DMAC	6 mL · 1:1 mixture	91 · S11.8.1 Synthesis procedure and activation
Solvent	DI water	1.5 mL for HATP.6HCl solution	91 · S11.8.1 Synthesis procedure and activation

Complete recipeSource: SI

Route 4: Drop Cast

70 · S11.1 Fabrication of the sensing devices · Figure S84

Metal precursorspreformed Ni3(HITP)2 particles from each 2D zone

Linker precursorsnot applicable; preformed framework suspension

Solventsdeionized water

Additivesnone reported

Atmosphereair drying; N2 during device conditioning/sensing

Temperature75 drying

Time2 h sonication; 0.667 h drying

Substrate orientation20 uL of 1 mg mL-1 aqueous MOF suspension drop-cast onto Metrohm 5 um gap gold interdigitated electrodes

Oxidant / reductantnone

Work-upDevices dried in preheated oven and resistance measured at room temperature under air.

ActivationNo additional device activation beyond MOF particle activation and device drying.

Scalability contextDevice fabrication used 2-4 devices for each zone in sensing tests.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni3(HITP)2 sample	0.5 mg dispersed; 20 uL drop-cast · 1 mg mL-1 suspension	70 · S11.1 Fabrication of the sensing devices · Figure S84
Solvent	deionized water	0.5 mL	70 · S11.1 Fabrication of the sensing devices · Figure S84
Other	gold interdigitated electrode	5 um gaps	70 · S11.1 Fabrication of the sensing devices · Figure S84

Complete recipeSource: SI

Route 5: Other

50 · S9.1 Synthetic procedure · Figure S64

Metal precursorsnickel acetate solution, 0.15 M

Linker precursorsHATP.6HCl, 0.03 M in DMF added to agar gel solution

Solventshot DI water and DMF; nickel solution 3:7 DMF:DI water

Additivesbacteriological agar; aqueous sodium acetate 5.85 M

Atmosphereambient air; no inert atmosphere reported

Temperature85 for agar dissolution; 80 for additional hydrogel stirring

Time36 h gelation; 240 h reaction/diffusion

Substrate orientation200 mL glass beaker, gel filled to two-thirds; outer electrolyte poured on top

Oxidant / reductantnone intentionally added

Work-upGel washed off using same procedure described in Section S2.

ActivationSame as Section S2 unless otherwise specified.

Scalability contextLarge-scale 1D/beaker reactor used to address limited surface area; main text reports larger 1D conversion of 11%.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel acetate solution	50 mL · 0.15 M	50 · S9.1 Synthetic procedure · Figure S64
Linker	HATP.6HCl	45 mL solution · 0.03 M in DMF	50 · S9.1 Synthetic procedure · Figure S64
Base	sodium acetate	25 mL aqueous solution · 5.85 M	50 · S9.1 Synthetic procedure · Figure S64
Additive	bacteriological agar	1.5 g · 1% w/w	50 · S9.1 Synthetic procedure · Figure S64
Solvent	DI water	80 mL hot DI water plus nickel solution water fraction	50 · S9.1 Synthetic procedure · Figure S64
Solvent	DMF	45 mL linker solution plus nickel solution DMF fraction	50 · S9.1 Synthetic procedure · Figure S64