cMOF Evidence Base

Synthesis evidence

Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by “4 + 2” Phenyl Ligands

Huang X., Fu S., Lin C. et al. · Journal of the American Chemical Society · 2023 · 2430-2438

5 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Liquid Liquid Interface

SI p. 2 · Synthesis of Cu4DHTTB

Metal precursorsCuSO4
Linker precursorsBHT ligand in toluene (implied by Cu3BHT film synthesis)
Solventswater; toluene; DMF; acetonitrile; methanol; acetone
Atmospherenot specified; dry under vacuum
Temperature80
Substrate orientationtransferred onto quartz/fused silica/SiO2 substrate
Work-upSame interfacial film procedure as Cu4DHTTB, followed by transfer and solvent rinsing.
Activationdry under vacuum at 80 C
Scalability contextFilm forms after several minutes at a liquid-liquid interface.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCuSO4Not specifiedSI p. 2 · Synthesis of Cu4DHTTB
LinkerBHT ligand1 mL toluene solution, inferred same generic method · 20 uM, inferred same generic methodSI p. 2 · Synthesis of Cu4DHTTB
Solventwater30 mLSI p. 2 · Synthesis of Cu4DHTTB
Solventtoluene30 mL buffer layer plus ligand solution solventSI p. 2 · Synthesis of Cu4DHTTB
Partial recipeSource: SI

Route 2: Liquid Liquid Interface

SI p. 2 · Synthesis of Cu4DHTTB

Metal precursorsCuSO4
Linker precursorsDHTTB ligand in toluene
Solventswater; toluene; DMF; acetonitrile; methanol; acetone
Atmospherenot specified; dry under vacuum
Temperature80
Substrate orientationtransferred onto quartz/fused silica/SiO2 substrate
Work-upAqueous CuSO4 solution covered with toluene buffer layer; 1 mL of 20 uM ligand solution injected into upper phase; film transferred to quartz substrate and rinsed with DMF, acetonitrile, methanol and acetone.
Activationdry under vacuum at 80 C
Scalability contextFilm forms after several minutes at a liquid-liquid interface.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCuSO4Not specifiedSI p. 2 · Synthesis of Cu4DHTTB
LinkerDHTTB ligand1 mL toluene solution · 20 uMSI p. 2 · Synthesis of Cu4DHTTB
Solventwater30 mLSI p. 2 · Synthesis of Cu4DHTTB
Solventtoluene30 mL buffer layer plus ligand solution solventSI p. 2 · Synthesis of Cu4DHTTB
Partial recipeSource: Both

Route 3: Hydrothermal

SI p. 2 · Synthesis of Cu4DHTTB

Metal precursorsCuSO4.5H2O
Linker precursorsDHTTB
Solventsdegassed water
Atmospherenitrogen
Temperature80
Time12
Oxidant / reductantCu(II) is inferred to oxidise DHTTB to a quinone derivative while being reduced to Cu(I)
Work-upFilter solid products, wash with dimethyl formamide, acetonitrile and source-reported 'menthol', dry under dynamic vacuum for 24 h.
Activationdynamic vacuum drying for 24 h
Scalability contextYield reported as 0.135 g, 91%; exact reagent amounts are not given.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCuSO4.5H2ONot specifiedSI p. 2 · Synthesis of Cu4DHTTB
LinkerDHTTBNot specifiedSI p. 2 · Synthesis of Cu4DHTTB
Solventdegassed waterNot specifiedSI p. 2 · Synthesis of Cu4DHTTB
Solventdimethyl formamidewash solventSI p. 2 · Synthesis of Cu4DHTTB
Solventacetonitrilewash solventSI p. 2 · Synthesis of Cu4DHTTB
Solventmentholwash solvent as written in SISI p. 2 · Synthesis of Cu4DHTTB
Partial recipeSource: SI

Route 4: Other

SI pp. 1-2 · Synthesis methods · Scheme S1

Linker precursors2,3,5,6-tetrakis(isopropylthio)benzene-1,4-dihydroquinone (2)
Solventsdried fluorobenzene; degassed water
AdditivesBBr3
Atmospherenitrogen for hydrolysis step
Temperature60
Time48
Oxidant / reductantBBr3 deprotection reagent
Work-upCool to room temperature, filter white DHTTB(BBr3) precipitate, wash with dry fluorobenzene, transfer under nitrogen, add degassed water, stir 1 h, suction filter, wash with cold water and dry under vacuum.
Activationvacuum drying
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Linker2,3,5,6-tetrakis(isopropylthio)benzene-1,4-dihydroquinone (2)Not specifiedSI pp. 1-2 · Synthesis methods · Scheme S1
OtherBBr3Not specifiedSI pp. 1-2 · Synthesis methods · Scheme S1
Solventdried fluorobenzeneNot specifiedSI pp. 1-2 · Synthesis methods · Scheme S1
Solventdegassed waterNot specifiedSI pp. 1-2 · Synthesis methods · Scheme S1
Partial recipeSource: SI

Route 5: Other

SI p. 1 · Synthesis methods · Scheme S1

Linker precursorsp-chloranil
Solventstoluene; Milli-Q water; hot methanol for recrystallisation
Additivessodium hydroxide; 2-propanethiol; anhydrous magnesium sulfate drying agent
Atmosphereambient temperature; atmosphere not otherwise specified
Temperature65
Time24
Oxidant / reductantp-chloranil precursor; 2-propanethiol substitution reagent
Work-upCool to ambient temperature, add 200 mL Milli-Q water, stir 1 h, separate organic layer, dry over anhydrous MgSO4, remove solvent and recrystallise residue from 150 mL hot methanol.
Scalability contextReported on 50 mmol p-chloranil scale.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Basesodium hydroxide10 g, 250 mmolSI p. 1 · Synthesis methods · Scheme S1
Other2-propanethiol22.85 g, 300 mmol, 28.21 mLSI p. 1 · Synthesis methods · Scheme S1
Otherp-chloranil12.94 g, 50 mmol · in 300 mL toluene solutionSI p. 1 · Synthesis methods · Scheme S1
Solventtoluene300 mL solution plus unspecified suspension volumeSI p. 1 · Synthesis methods · Scheme S1
SolventMilli-Q water200 mLSI p. 1 · Synthesis methods · Scheme S1
Solventmethanol150 mLSI p. 1 · Synthesis methods · Scheme S1