cMOF Evidence Base

Synthesis evidence

Conductivity, doping, and redox chemistry of a microporous dithiolene-based metal-organic framework

Kobayashi Y., Jacobs B., Allendorf M.D. et al. · Chemistry of Materials · 2010 · 4120-4122

15 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Other

3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]

Metal precursorsNa[Cu(pdt)2] and CuI
Linker precursorspdt2- already incorporated in Na[Cu(pdt)2]
SolventsAcetonitrile
Temperatureroom temperature not explicitly stated
Oxidant / reductantCuI functions as Cu source for framework assembly
Work-upPrepared analogously to Cu[Ni(pdt)2], yielding rough micron-sized particles.
ActivationAs-synthesised sample remains solvated; desolvation causes collapse.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceNa[Cu(pdt)2]Not specified3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]
Metal SourceCuINot specified3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]
SolventacetonitrileNot specified3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]
Vague recipeSource: Main

Route 2: Drop Cast

3 · Electrochemistry · Figure 4

Metal precursorsCu[Cu(pdt)2] particles
Linker precursorspdt2- already incorporated
SolventsSuspension solvent not specified
Substrate orientationPt disk electrode
Work-upParticles cast onto Pt disk; framework later removed by polishing for control.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
OtherCu[Cu(pdt)2] particlesNot specified3 · Electrochemistry · Figure 4
Complete recipeSource: Main

Route 3: Other

2 · Iodine doping

Metal precursorsI2-doped Cu[Ni(pdt)2] film
Linker precursorspdt2- already incorporated
AdditivesAir exposure
AtmosphereAir
Temperatureroom temperature
Time12
Substrate orientationFilm on Pt IDE
Oxidant / reductantPartial de-doping/reversal inferred
Work-upConductivity measured after exposure.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
Otherair12 h exposure2 · Iodine doping
Complete recipeSource: Both

Route 4: Other

4 · Doping and Conductivity Measurements

Metal precursorsSolvated Cu[Ni(pdt)2]
Linker precursorspdt2- already incorporated
AtmosphereDynamic vacuum
Temperature120
Time2
Work-upHeat under dynamic vacuum; retain crystallinity by PXRD.
Activation120 degC under dynamic vacuum for 2 h in conductivity apparatus or powder activation.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
Othersolvated Cu[Ni(pdt)2]Not specified4 · Doping and Conductivity Measurements
Complete recipeSource: Both

Route 5: Other

3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]

Metal precursorsNa[Ni(pdt)2] and CuI
Linker precursorspdt2- already incorporated in Na[Ni(pdt)2]
SolventsAcetonitrile
Temperatureroom temperature not explicitly stated
Oxidant / reductantCuI functions as Cu source for framework assembly
Work-upCuI/acetonitrile solution added dropwise under rapid stirring; dark red colloid filtered on 0.22 um nylon membrane filter.
ActivationAs-synthesised sample remains solvated.
Scalability contextTypical preparation used 0.60 g Na[Ni(pdt)2] and 0.29 g CuI.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceNa[Ni(pdt)2]0.60 g, 0.0015 mol3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]
Metal SourceCuI0.29 g, 0.0015 mol3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]
Solventacetonitrile200 mL plus 15 mL3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2]
Complete recipeSource: Both

Route 6: Other

4 · Doping and Conductivity Measurements

Metal precursorsDesolvated Cu[Ni(pdt)2] film
Linker precursorspdt2- already incorporated
AdditivesIodine vapour
AtmosphereFlowing N2/I2
Temperature50
Substrate orientationFilm on Pt IDE in heated tube
Oxidant / reductantI2 oxidant
Work-upConductivity recorded during exposure; no air exposure before measurement.
ActivationFilm first heated to 120 degC and held under vacuum for 2 h to desolvate.
Scalability contextIodine vapour generated from granulated iodine at room temperature; PI2 = 0.34 torr; N2 = 75 mL/min; iodine delivery ca. 1.5 umol/min or 23 mg/h.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Oxidantgranulated iodinePI2 = 0.34 torr; approx. 1.5 umol/min or 23 mg/hr delivered4 · Doping and Conductivity Measurements
OtherN2 carrier gas75 mL/min4 · Doping and Conductivity Measurements
Partial recipeSource: Both

Route 7: Other

2 · Iodine doping · Figure 3

Metal precursorsDesolvated Cu[Ni(pdt)2] film
Linker precursorspdt2- already incorporated
AdditivesIodine vapour
AtmosphereFlowing N2/I2
Temperature150
Substrate orientationFilm on Pt IDE in heated tube
Oxidant / reductantI2 oxidant
Work-upConductivity recorded during exposure.
ActivationFilm first desolvated under the conductivity-protocol vacuum treatment.
Scalability contextUses the same iodine-vapour apparatus as 50 degC doping; exact duration for the 150 degC trace is not stated outside Figure 3.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
Oxidantiodine vapourPI2 = 0.34 torr in shared apparatus2 · Iodine doping · Figure 3
Complete recipeSource: SI

Route 8: Drop Cast

3-4 · Preparation of Cu[Ni(pdt)2] electrodes

Metal precursorsCu[Ni(pdt)2] powder
Linker precursorspdt2- already incorporated
SolventsAcetonitrile
Temperature50
Timeovernight
Substrate orientationIDE in a tilted vial, electrode at 45 degrees
Work-upSlow evaporation; excess film scraped off with soft plastic before measurement.
ActivationDesolvated before conductivity measurement as described in the conductivity protocol.
Scalability context11 mg Cu[Ni(pdt)2] in 2.5 mL acetonitrile for one tall 5 mL vial containing an IDE.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherCu[Ni(pdt)2]11 mg3-4 · Preparation of Cu[Ni(pdt)2] electrodes
Solventacetonitrile2.5 mL3-4 · Preparation of Cu[Ni(pdt)2] electrodes
Partial recipeSource: SI

Route 9: Drop Cast

4 · Preparation of Cu[Ni(pdt)2] electrodes

Metal precursorsCu[Ni(pdt)2] powder
Linker precursorspdt2- already incorporated
SolventsAcetonitrile
Temperature50 by analogy to IDE route
Timeovernight by analogy to IDE route
Substrate orientationITO slides cut to suitable sizes
Work-upDeposited in a similar manner to IDE films.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherCu[Ni(pdt)2]Not specified4 · Preparation of Cu[Ni(pdt)2] electrodes
SolventacetonitrileNot specified4 · Preparation of Cu[Ni(pdt)2] electrodes
Partial recipeSource: SI

Route 10: Other

3 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2

Metal precursorsCuCl2.2H2O
Linker precursorsPyrazine-2,3-dithiol
SolventsAnalogous to nickel route: methanol, ethanol, water, chloroform
AdditivesSodium ethoxide; tetrabutylammonium bromide adjusted to half the nickel-route amount
Work-upAnalogous to nickel tetrabutylammonium complex workup.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCuCl2.2H2ONot specified3 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Additivetetrabutylammonium bromidehalf the nickel-route amount3 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Vague recipeSource: Main

Route 11: Drop Cast

3 · Electrochemistry · Figure 4

Metal precursorsCu[Ni(pdt)2] or Cu[Cu(pdt)2] particles
Linker precursorspdt2- already incorporated
SolventsSuspension solvent not specified
Substrate orientationPt disk electrode
Work-upParticles cast onto Pt disk; framework later removed by polishing for control.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
OtherCu[Ni(pdt)2] particlesNot specified3 · Electrochemistry · Figure 4
Partial recipeSource: SI

Route 12: Other

3 · Na[Ni(pdt)2].2H2O and Na[Cu(pdt)2].2H2O

Metal precursorsNa[Cu(pdt)2] prepared according to Ribas et al.
Linker precursorspdt ligand
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
Metal SourceNa[Cu(pdt)2]Not specified3 · Na[Ni(pdt)2].2H2O and Na[Cu(pdt)2].2H2O
Partial recipeSource: SI

Route 13: Other

3 · Na[Ni(pdt)2].2H2O and Na[Cu(pdt)2].2H2O

Metal precursorsNiClO4.6H2O
Linker precursorspdt ligand, following Ribas et al.
AdditivesSodium source from Ribas procedure
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
Metal SourceNiClO4.6H2ONot specified3 · Na[Ni(pdt)2].2H2O and Na[Cu(pdt)2].2H2O
Complete recipeSource: SI

Route 14: Other

2 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2

Metal precursorsAnhydrous NiCl2
Linker precursorsPyrazine-2,3-dithiol
SolventsMethanol, absolute ethanol, water, chloroform
AdditivesSodium ethoxide; tetrabutylammonium bromide
Work-upMethanol removed in vacuo; redissolved in ethanol and filtered; ethanol removed; extracted with chloroform; organic layers washed with water, dried over Na2SO4, evaporated.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Linkerpyrazine-2,3-dithiol1.6 g, 0.011 mol2 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Basesodium ethoxide1.6 g, 0.022 mol · 95% purity2 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Metal Sourceanhydrous NiCl20.72 g, 0.0056 mol2 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Additivetetrabutylammonium bromide0.61 g, 0.0019 mol, 0.8 equiv. · slight deficit2 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Solventmethanol20 mL plus 20 mL2 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Solventabsolute ethanol300 mL2 · (Bu4N)2Ni(pdt)2 and (Bu4N)Cu(pdt)2
Complete recipeSource: SI

Route 15: Other

2 · Pyrazine-2,3-dithiolene

Linker precursorsPyrazine-2,3-dichloride; sodium hydrosulfide hydrate
SolventsDeoxygenated methanol; deoxygenated water
AdditivesAqueous hydrochloric acid
AtmosphereDeoxygenated solvents
Temperaturereflux, then room temperature, then -20
Timeovernight reflux; overnight cooling at room temperature; overnight at -20 degC
Oxidant / reductantSodium hydrosulfide hydrate as sulfur/nucleophilic reagent
Work-upCold methanol wash; collected dark red crystals
Scalability contextYield reported as 2.3 g, 43%.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Linkerpyrazine-2,3-dichloride5.7574 g, 0.036713 mol · 95% purity2 · Pyrazine-2,3-dithiolene
Additivesodium hydrosulfide hydrate21.328 g, 0.19371 mol, 2.6 equiv. · 95% purity2 · Pyrazine-2,3-dithiolene
Solventdeoxygenated methanol100 mL plus 300 mL2 · Pyrazine-2,3-dithiolene
Solventdeoxygenated water200 mL2 · Pyrazine-2,3-dithiolene
Acidaqueous hydrochloric acid100 mL and 50 mL · 1.8 M and 1 M2 · Pyrazine-2,3-dithiolene