Synthesis · Colloidal crystal engineering with metal–organic framework nanoparticles and DNA

9 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

11 · Preparation of PCN-222 superlattice stabilized with Ag+

Metal precursorsassembled PCN-222 superlattice

Linker precursorsDNA linkers already present in assembled PCN-222 superlattice

Solventsaqueous 0.5 M NaClO4 with 0.01 wt% SDS; 0.5 M AgNO3 aqueous solution; water; methanol

AdditivesAgNO3; NaClO4; SDS

Atmospheredark during AgNO3 incubation

Temperatureroom temperature

Time12

Oxidant / reductantAg+ stabilising ion

Work-upSolvent-exchanged with aqueous NaClO4/SDS three times, treated with AgNO3, then solvent-exchanged with water and methanol three times.

Activationnot reported

Scalability contextPost-synthetic stabilisation of pre-formed superlattice; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	assembled PCN-222 superlattice	Not specified	11 · Preparation of PCN-222 superlattice stabilized with Ag+
Additive	NaClO4	solvent exchange three times · 0.5 M	11 · Preparation of PCN-222 superlattice stabilized with Ag+
Additive	SDS	0.01 wt%	11 · Preparation of PCN-222 superlattice stabilized with Ag+
Additive	AgNO3	rapidly added · 0.5 M aqueous solution	11 · Preparation of PCN-222 superlattice stabilized with Ag+

Complete recipeSource: SI

Route 2: Solvothermal

4 · Synthesis of octahedral UiO-66 NPs

Metal precursorszirconyl chloride octahydrate (21 mg, 66 umol)

Linker precursors1,4-benzenedicarboxylic acid (10 mg, 60 umol)

SolventsDMF: 0.2 mL for linker plus 3 mL for metal salt

Additivesacetic acid (0.5 mL)

Atmospherenot reported

Temperature90

Time5

Work-upCollected by centrifugation at 10000 rpm for 20 min, solvent-exchanged with DMF, stored in anhydrous DMF.

Activationnot reported

Scalability contextSmall vial solvothermal synthesis; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconyl chloride octahydrate	21 mg, 66 umol	4 · Synthesis of octahedral UiO-66 NPs
Linker	1,4-benzenedicarboxylic acid	10 mg, 60 umol	4 · Synthesis of octahedral UiO-66 NPs
Solvent	DMF	3.2 mL total	4 · Synthesis of octahedral UiO-66 NPs
Acid	acetic acid	0.5 mL	4 · Synthesis of octahedral UiO-66 NPs

Complete recipeSource: SI

Route 3: Solvothermal

4 · Synthesis of PCN-222/MOF-545 NPs

Metal precursorszirconyl chloride octahydrate (38 mg, 0.12 mmol)

Linker precursorstetrakis(4-carboxyphenyl)-porphyrin (6.5 mg, 0.0082 mmol)

SolventsDMF (16 mL)

Additivesdichloroacetic acid (0.30 mL, 3.0 mmol)

Atmospheresealed borosilicate vial with Teflon-lined cap; atmosphere not otherwise reported

Temperature130

Time18

Work-upCollected by centrifugation at 12000 rpm for 30 min, solvent-exchanged with DMF, stored in anhydrous DMF.

Activationnot reported

Scalability context22 mL vial synthesis; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconyl chloride octahydrate	38 mg, 0.12 mmol	4 · Synthesis of PCN-222/MOF-545 NPs
Linker	tetrakis(4-carboxyphenyl)-porphyrin	6.5 mg, 0.0082 mmol	4 · Synthesis of PCN-222/MOF-545 NPs
Solvent	DMF	16 mL	4 · Synthesis of PCN-222/MOF-545 NPs
Acid	dichloroacetic acid	0.30 mL, 3.0 mmol	4 · Synthesis of PCN-222/MOF-545 NPs

Complete recipeSource: SI

Route 4: Other

6 · DNA functionalization of MOF NPs

Metal precursorsPCN-222 nanorods (14.1 pmol for PEG step; 2 pmol for DNA step)

Linker precursorsphosphate-PEG5k-N3 linker; DBCO-TEG modified DNA

SolventsDMF, 1:1 DMF/water, water

AdditivesNaCl slowly added to 0.5 M

Atmospherenot reported

Temperature25

Time>48

Work-upWashed with DMF, 1:1 DMF/water and water; excess DNA removed by centrifugation and resuspension.

Activationnot applicable

Scalability contextNanorod functionalisation on pmol-particle scale; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PCN-222 nanorods	14.1 pmol for PEG step; 2 pmol for DNA step · 2 nM during DNA step	6 · DNA functionalization of MOF NPs
Linker	phosphate-PEG5k-N3 linker	5 mg in 50 uL linker solution	6 · DNA functionalization of MOF NPs
Linker	DBCO-TEG modified DNA	200 nmol in 1 mL water · 0.2 mM	6 · DNA functionalization of MOF NPs
Additive	NaCl	added over 8 h · 0.5 M final	6 · DNA functionalization of MOF NPs

Complete recipeSource: SI

Route 5: Solvothermal

3-4 · Synthesis of spherical UiO-66 NPs

Metal precursorszirconyl chloride octahydrate (21 mg, 66 umol)

Linker precursors1,4-benzenedicarboxylic acid (25 mg, 0.25 mmol)

SolventsDMF: 0.5 mL for linker plus 3 mL for metal salt

Additivesacetic acid (0.5 mL)

Atmospherenot reported

Temperature90

Time6

Work-upCollected by centrifugation at 12000 rpm for 30 min, solvent-exchanged with DMF, stored in anhydrous DMF.

Activationnot reported

Scalability contextSmall 10 mL scintillation vial synthesis; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconyl chloride octahydrate	21 mg, 66 umol	3-4 · Synthesis of spherical UiO-66 NPs
Linker	1,4-benzenedicarboxylic acid	25 mg, 0.25 mmol	3-4 · Synthesis of spherical UiO-66 NPs
Solvent	DMF	3.5 mL total	3-4 · Synthesis of spherical UiO-66 NPs
Acid	acetic acid	0.5 mL	3-4 · Synthesis of spherical UiO-66 NPs

Complete recipeSource: SI

Route 6: Other

8 · Synthesis of MOF-Au CsCl hybrid superlattice

Metal precursorsDNA functionalized 40 nm AuNPs and 37 nm UiO-66 NPs, 1:1 ratio

Linker precursorscomplementary linker A (2000 equivalents) and complementary linker B (1000 equivalents)

Solventsaqueous 0.02% SDS and 0.5 M NaCl

AdditivesSDS; NaCl

Atmospherenot reported

Temperatureheated above melting temperature, then cooled to 20 deg C

Work-upEach mixture incubated 20 min; 50 uL of each solution combined; aggregates annealed in PCR system.

Activationnot applicable

Scalability contextSmall solution assembly; no scale-up reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	DNA functionalized 40 nm AuNPs	50 uL solution combined · 10 nM	8 · Synthesis of MOF-Au CsCl hybrid superlattice
Other	DNA functionalized 37 nm UiO-66 NPs	50 uL solution combined · 10 nM	8 · Synthesis of MOF-Au CsCl hybrid superlattice
Linker	complementary linker A	2000 equivalents	8 · Synthesis of MOF-Au CsCl hybrid superlattice
Linker	complementary linker B	1000 equivalents	8 · Synthesis of MOF-Au CsCl hybrid superlattice
Additive	SDS and NaCl	0.02% SDS; 0.5 M NaCl	8 · Synthesis of MOF-Au CsCl hybrid superlattice

Complete recipeSource: SI

Route 7: Other

8 · Synthesis of MOF-MOF bcc superlattice

Metal precursorsDNA functionalized 37 nm UiO-66 NP A and NP B, 1:1 ratio

Linker precursorscomplementary linker A (1000 equivalents) and complementary linker B (1000 equivalents)

Solventsaqueous 0.02% SDS and 0.5 M NaCl

AdditivesSDS; NaCl

Atmospherenot reported

Temperatureheated above melting temperature, then cooled to 20 deg C

Work-upEach linker/NP mixture incubated 20 min, 50 uL of each combined, aggregates annealed in PCR system.

Activationnot applicable

Scalability contextSmall solution assembly; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	DNA functionalized 37 nm UiO-66 NP A and B	50 uL of each solution combined · 20 nM each	8 · Synthesis of MOF-MOF bcc superlattice
Linker	complementary linker A	1000 equivalents	8 · Synthesis of MOF-MOF bcc superlattice
Linker	complementary linker B	1000 equivalents	8 · Synthesis of MOF-MOF bcc superlattice
Additive	SDS and NaCl	0.02% SDS; 0.5 M NaCl	8 · Synthesis of MOF-MOF bcc superlattice

Complete recipeSource: SI

Route 8: Other

7-8 · Synthesis of MOF fcc superlattice

Metal precursorsDNA functionalized 37 nm UiO-66 NPs

Linker precursorsself-complementary DNA linker, 2000 equivalents

Solventsaqueous 0.02% SDS and 0.5 M NaCl

AdditivesSDS; NaCl

Atmospherenot reported

Temperatureheated to a few degrees above melting temperature (55 deg C), then cooled to 20 deg C

Work-upAggregates settled within minutes; thermally annealed in a ProFlex PCR system.

Activationnot applicable

Scalability contextSmall solution assembly; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	DNA functionalized 37 nm UiO-66 NPs	50 nM	7-8 · Synthesis of MOF fcc superlattice
Linker	self-complementary DNA linker	2000 equivalents	7-8 · Synthesis of MOF fcc superlattice
Additive	SDS	0.02%	7-8 · Synthesis of MOF fcc superlattice
Additive	NaCl	0.5 M	7-8 · Synthesis of MOF fcc superlattice

Complete recipeSource: SI

Route 9: Other

6-7 · DNA functionalization of MOF NPs

Metal precursors37 nm UiO-66 NPs (33 pmol, ca. 2 x 10^13 particles)

Linker precursorsphosphate-PEG5k-N3 linker; DBCO-TEG modified DNA

SolventsDMF, 1:1 DMF/water, water

AdditivesNaCl slowly added to 0.5 M; 0.02% SDS used in later assembly conditions

Atmospherenot reported

Temperature25

Time>48

Work-upWashed with DMF, sequentially with 1:1 DMF/water, twice with water; excess DNA removed by 5 centrifugation cycles at 5000 rpm for 10 min and resuspension in water.

Activationnot applicable

Scalability contextNanoparticle functionalisation on pmol-particle scale; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	37 nm UiO-66 NPs	33 pmol, ca. 2 x 10^13 particles · 33 nM during DNA step	6-7 · DNA functionalization of MOF NPs
Linker	phosphate-PEG5k-N3 linker	10 mg in 100 uL DMF · ca. 20 mM	6-7 · DNA functionalization of MOF NPs
Linker	DBCO-TEG modified DNA	300 nmol in 1 mL water · 0.3 mM	6-7 · DNA functionalization of MOF NPs
Additive	NaCl	added over 8 h · 0.5 M final	6-7 · DNA functionalization of MOF NPs