Synthesis evidence

Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers

Huang X., Li Y., Fu S. et al. · Angewandte Chemie - International Edition · 2024 · e202320091

6 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Liquid Liquid Interface

SI p.2 · Interface synthesis of Ag4TTBQ

Metal precursorssilver nitrate (AgNO3)
Linker precursorsTTHQ, oxidised in situ to TTBQ
Solventschlorobenzene and water
Additiveswater buffer layer
Atmospherenot specified for the interfacial reaction; solvents degassed before use
Temperature70
Time48
Substrate orientationchlorobenzene/water liquid-liquid interface
Oxidant / reductantIn situ HNO3 generated from AgNO3/protons oxidises TTHQ to TTBQ before coordination.
Work-upBlack interfacial film sonicated into nanocrystals; washed with DMF, water, methanol and diethyl ester.
Scalability context85 mg product, 63% yield.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTTHQ48mg, 0.2mmolSI p.2 · Interface synthesis of Ag4TTBQ
Metal SourceAgNO3116.8 mg, 0.7 mmol in 5 mL aqueous solutionSI p.2 · Interface synthesis of Ag4TTBQ
Solventchlorobenzene50 mlSI p.2 · Interface synthesis of Ag4TTBQ
Solventpure water100 ml buffer layerSI p.2 · Interface synthesis of Ag4TTBQ
Oxidantin situ generated HNO3 from AgNO3/protonsdiluteSI p.2 · Interface synthesis of Ag4TTBQ
Complete recipeSource: SI

Route 2: Drop Cast

SI p.7 · Ultrafast THz spectroscopy · Figure S11

Metal precursorspreformed Ag4TTBQ powder
Solventswater/ethylene glycol (4:1 v/v)
Atmospheredry N2 during THz measurement
Time1 h ultrasonication
Substrate orientationfused silica/fused silicon substrate
Work-updrop-cast well-dispersed suspension to form translucent film
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherAg4TTBQ powder1 mgSI p.7 · Ultrafast THz spectroscopy · Figure S11
Solventwater and ethylene glycol100 uL · v/v=4:1SI p.7 · Ultrafast THz spectroscopy · Figure S11
Complete recipeSource: Both

Route 3: Other

SI p.1 · One-pot synthesis of Ag4TTHQ

Metal precursorssilver acetate (AgOAc)
Linker precursorsTTHQ
Solventsdegassed methanol
Atmosphereargon atmosphere/protection
Temperature70
Time12
Oxidant / reductantAgOAc generates acetic acid without oxidising ability; TTHQ remains in hydroquinone oxidation state.
Work-upSolid precipitate collected by filtration; washed with dimethylformamide, water, methanol and diethyl ether.
Activationdried under vacuum at 85 deg C for 12 h
Scalability context117.5 mg product, 88% yield.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTTHQ48mg, 0.2mmolSI p.1 · One-pot synthesis of Ag4TTHQ
Metal Sourcesilver acetate116.8mg, 0.7 mmolSI p.1 · One-pot synthesis of Ag4TTHQ
Solventdegassed methanol40-degassed methanolSI p.1 · One-pot synthesis of Ag4TTHQ
Complete recipeSource: SI

Route 4: Drop Cast

SI p.7 · Ultrafast THz spectroscopy · Figure S11

Metal precursorspreformed Ag4TTHQ powder
Solventswater/ethylene glycol (4:1 v/v)
Atmospheredry N2 during THz measurement
Time1 h ultrasonication
Substrate orientationfused silica/fused silicon substrate
Work-updrop-cast well-dispersed suspension to form translucent film
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherAg4TTHQ powder1 mgSI p.7 · Ultrafast THz spectroscopy · Figure S11
Solventwater and ethylene glycol100 uL · v/v=4:1SI p.7 · Ultrafast THz spectroscopy · Figure S11
Partial recipeSource: Both

Route 5: Other

SI p.2 · One-pot synthesis trial by using AgNO3 · Figures S15-S16

Metal precursorssilver nitrate (AgNO3)
Linker precursorsTTHQ
Solventsdegassed methanol
Atmospherenot specified
Oxidant / reductantNO3- facilitates HNO3 formation and in situ oxidation, but concurrent phases form.
Work-upnot specified
Scalability contextFailed to yield a pure phase.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTTHQNot specifiedSI p.2 · One-pot synthesis trial by using AgNO3 · Figures S15-S16
Metal SourceAgNO3Not specifiedSI p.2 · One-pot synthesis trial by using AgNO3 · Figures S15-S16
Solventdegassed methanolNot specifiedSI p.2 · One-pot synthesis trial by using AgNO3 · Figures S15-S16
Partial recipeSource: SI

Route 6: Other

SI p.1 · Materials · Scheme S1

Linker precursorsp-chloranil; 2-propanethiolate; 2,3,5,6-tetrakis(isopropylthio)benzene-1,4-dihydroquinone intermediate
Solventstoluene; fluorobenzene; degassed water according to Scheme S1
AdditivesBBr3
Atmospherenot fully specified in SI summary
Temperature65 deg C for 24 h; 60 deg C for 48 h; room temperature for 30 min in Scheme S1
Time24 h; 48 h; 0.5 h
Oxidant / reductantBBr3 Lewis acid deprotection followed by hydrolysis
Work-upHydrolysis to obtain TTHQ; full isolation details deferred to previous report.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Linkerp-chloranilNot specifiedSI p.1 · Materials · Scheme S1
Additive2-propanethiolateNot specifiedSI p.1 · Materials · Scheme S1
AdditiveBBr3Not specifiedSI p.1 · Materials · Scheme S1
Solventtoluene; fluorobenzene; water (degassed)Not specifiedSI p.1 · Materials · Scheme S1