cMOF Evidence Base

Synthesis evidence

Large Single Crystals of Two-Dimensional π-Conjugated Metal-Organic Frameworks via Biphasic Solution-Solid Growth

Ha D.-G., Rezaee M., Han Y. et al. · ACS Central Science · 2021 · 104-109

7 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Vague recipeSource: SI

Route 1: Hydrothermal

S23 · Figure caption · Figure S18

Metal precursorsNot specified in this paper
Linker precursorsNot specified in this paper
SolventsNot specified
AdditivesNot specified
AtmosphereNot specified
Substrate orientationNot applicable
Oxidant / reductantNot specified
Work-upNot specified
ActivationNot specified
Scalability contextNot discussed
Complete recipeSource: Both

Route 2: Other

S22 · Figure caption · Figure S17

Metal precursorsCobalt acetate replacing nickel acetate under otherwise identical growth conditions
Linker precursorsHHTP film as in Ni-CAT-1 typical route
SolventsMethanol for metal acetate deposition; water reaction medium; workup not separately specified
AdditivesTeflon-coated magnets as in typical route
AtmosphereLoosely capped vial presumed from identical Ni route; no inert atmosphere specified
Temperature95 inferred from identical Ni-CAT-1 growth conditions
Time12 inferred from typical Ni-CAT-1 growth conditions unless otherwise varied
Substrate orientationIdentical to Ni-CAT-1 solution-solid arrangement except cobalt acetate metal source
Oxidant / reductantNone specified
Work-upNot separately specified; presumed water/DMF wash as for Ni route
ActivationNone reported
Scalability contextDemonstrates applicability of method to Co-CAT-1; no yield table reported for Co analogue.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcecobalt acetatesame as Ni-CAT-1 route inferred · 10 mM methanol solution inferredS22 · Figure caption · Figure S17
LinkerHHTP40-nm-thick film inferred from typical routeS22 · Figure caption · Figure S17
Solventwater4~10 mL inferredS22 · Figure caption · Figure S17
SolventmethanolNot specifiedS22 · Figure caption · Figure S17
Partial recipeSource: SI

Route 3: Drop Cast

S9 · Figure caption · Figure S4

Metal precursorsNickel acetate as in typical solution-solid route
Linker precursorsDrop-cast HHTP film, 10 uL of 1.7 mM methanol solution drop-cast twice
SolventsMethanol for HHTP and nickel acetate deposition; water reaction medium
AdditivesNone beyond standard magnets/substrates
AtmosphereNot specified; same as typical route
Temperature95 presumed as typical route
TimeNot specified for this control
Substrate orientationRandomly oriented polycrystalline drop-cast HHTP replaces evaporated aligned HHTP
Oxidant / reductantNone specified
Work-upNot separately specified; presumed same as typical route
ActivationNone reported
Scalability contextControl yielded few crystals over four independent trials, unlike evaporated HHTP which gave many micrometre-scale crystals each run.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerHHTP10 uL drop-cast twice · 1.7 mM methanol solutionS9 · Figure caption · Figure S4
Metal SourceNickel acetateas typical route · 10 mM methanol solution presumedS9 · Figure caption · Figure S4
SolventMethanolNot specifiedS9 · Figure caption · Figure S4
SolventWaterNot specifiedS9 · Figure caption · Figure S4
Partial recipeSource: SI

Route 4: Other

S11 · Figure caption · Figure S6

Metal precursorsNickel acetate as in typical route
Linker precursors40-nm-thick HHTP film
SolventsWater reaction medium; methanol deposition solvent
AdditivesDispersed microspheres with diameters 4 um, 9 um, or 49 um
AtmosphereNot specified
Temperature95 presumed as typical route
TimeNot specified
Substrate orientationSubstrate gap intentionally increased with microspheres
Oxidant / reductantNone specified
Work-upNot specified
ActivationNone reported
Scalability context49 um and 9 um gaps produced long/wire-shaped crystals and no plates; 4 um gap produced some low-yield, low-quality plates.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerHHTP40-nm-thick filmS11 · Figure caption · Figure S6
Metal SourceNickel acetateas typical routeS11 · Figure caption · Figure S6
Additivemicrospheresdispersed between substrates · 4, 9, or 49 um diameterS11 · Figure caption · Figure S6
Vague recipeSource: SI

Route 5: Hydrothermal

S14 · Figure caption · Figure S9

Metal precursorsNot specified in this paper; reported hydrothermal method cited
Linker precursorsNot specified in this paper; HHTP implied by Ni3(HHTP)2 identity
SolventsNot specified
AdditivesNot specified
AtmosphereNot specified
Substrate orientationNot applicable for powder
Oxidant / reductantNot specified
Work-upNot specified
ActivationNot specified; SI notes possible structural changes upon activation/evacuation in prior reports
Scalability contextNot discussed
Complete recipeSource: Both

Route 6: Other

S2 · Materials and Methods - Details of growth methods · Figure 1C

Metal precursorsNickel acetate; typical 20 uL of 10 mM methanol solution in main/caption; SI stock 10 mg in 4 mL methanol, 10 uL drop-cast 1-4 times
Linker precursorsHHTP, vacuum-evaporated as horizontally aligned film, typical 40 nm with line pattern
SolventsMethanol for Ni(OAc)2 drop-casting; 4-10 mL Milli-Q water as reaction medium; water and DMF wash
AdditivesTeflon-coated neodymium magnets; optional line-pattern shadow mask; no chemical additive for typical route
AtmosphereLoosely capped vial in oven; no inert atmosphere specified
Temperature95
Time12 typical; controls from 0.5 to 12 h
Substrate orientationTwo half-inch Si/SiO2 substrates pressed face-to-face, one bearing HHTP film and one nickel acetate film; HHTP film horizontally aligned; confined reaction space <1 uL / <4-6 um gap
Oxidant / reductantNone specified
Work-upCool naturally to room temperature; wash substrates in water and DMF; crystal plates mostly remain on HHTP substrate
ActivationNo activation step reported for single-crystal plates before characterisation
Scalability contextTypical growth gives micrometre-scale plates reproducibly; >10 um crystals occur occasionally and become more likely from thicker HHTP films; Table S2 quantifies yield by size bin.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
LinkerHHTP (95%)40-nm-thick film typical · deposited at 0.3~2 A/s below 1x10-6 TorrS2 · Materials and Methods - Details of growth methods · Figure 1C
Metal SourceNickel acetate (99.999%)20 uL typical in main; SI: 10 uL drop-cast 1~4 times · 10 mM methanol solution typical; SI stock 10 mg in 4 mL methanolS2 · Materials and Methods - Details of growth methods · Figure 1C
SolventMethanol4 mL for nickel acetate stockS2 · Materials and Methods - Details of growth methods · Figure 1C
SolventMilli-Q water4~10 mL in 20-mL vialS2 · Materials and Methods - Details of growth methods · Figure 1C
OtherTeflon-coated magnetstwo magnets pressing substrates; main text gives 50 kPaS2 · Materials and Methods - Details of growth methods · Figure 1C
Partial recipeSource: SI

Route 7: Other

S10 · Figure caption · Figure S5

Metal precursorsNickel acetate as in typical route
Linker precursorsHHTP film that dissolves in cosolvent
SolventsWater-DMF(30%) cosolvent
AdditivesNone specified
AtmosphereNot specified
Temperature95 presumed as typical route
TimeNot specified
Substrate orientationHHTP no longer remains as oriented solid film; solution-phase reaction dominates
Oxidant / reductantNone specified
Work-upNot specified
ActivationNone reported
Scalability contextNo crystal plates were observed; rod-shaped crystals formed.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerHHTPnot specifiedS10 · Figure caption · Figure S5
Metal SourceNickel acetateas typical routeS10 · Figure caption · Figure S5
Solventwater-DMF(30%) cosolventnot specified · 30% DMFS10 · Figure caption · Figure S5