Synthesis evidence

Macrocycle-Based Metal-Organic Frameworks with NO2-Driven On/Off Switch of Conductivity

Ma Y.-X., Gao B., Li Y. et al. · ACS Applied Materials and Interfaces · 2021 · 27066-27073

6 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

SI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1

Metal precursorsnone
Linker precursors2,6-dihydroxytoluene; paraldehyde; CH2ClBr; dimethyl 5-hydroxyisophthalate; compound intermediates 1-4
Solventswater, ethanol, DMF, CCl4, dichloromethane, acetonitrile, CH2Cl2/EtOH, THF/H2O
Additives37% HCl, K2CO3, N-bromosuccinimide, AIBN, nitric acid
AtmosphereN2 protection for compound 2, compound 4, and H8L steps; not stated for compound 1 and 3 except reflux.
Temperature80; 80; reflux in CCl4; 80; 75
Time16; 8; 8; 27; 12
Oxidant / reductantN-bromosuccinimide/AIBN bromination in compound 3 step; nitric acid used for acidification to pH about 1 in final H8L step.
Work-upWashing with cold ethanol-water, extraction with saturated NaCl, drying over Na2SO4, silica gel chromatography, recrystallisation from CH2Cl2/EtOH, water wash, THF evaporation, acidification and water evaporation.
Activationnot applicable
Scalability contextMultigram ligand precursor synthesis reported with yields for intermediates and final H8L.
Show 12 structured reagent records
RoleReagentAmount / concentrationSource
Linker2,6-dihydroxytoluene10.28 g, 80 mmolSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Otherparaldehyde3.53 g, 80 mmolSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Acid37% aqueous HCl50 mL · 37%SI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Solventwater100 mLSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Solventethanol100 mLSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Baseanhydrous K2CO325.06 g, 181.5 mmol; 2.5 g, 18 mmol; 5.56 g, 40 mmolSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
AdditiveCH2ClBr20 mLSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
OxidantN-bromosuccinimide (NBS)11.84 g, 66.3 mmolSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Additiveazodiisobutyronitrile (AIBN)catalytic amountSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Linkerdimethyl 5-hydroxyisophthalate3.78 g, 18 mmolSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Solventtetrahydrofuran (THF)400 mLSI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Acidnitric acidacidified until pH about 1SI pp.3-4 · Synthesis of compound 1; Synthesis of compound 2; Synthesis of compound 3; Synthesis of compound 4; Synthesis of H8L · Figure S1
Complete recipeSource: Both

Route 2: Other

main p.6 · Conversion Experiments · Figure S4

Metal precursorsMOF A Co framework
Linker precursorsMOF A calix[4]resorcinarene framework
Solventsnone added; water desorbed from channels
Additivesnone
Atmosphereoven; air/vacuum not fully specified
Temperature100
Time0.0833
Oxidant / reductantnone
Work-upSample can be exposed to air and cooled to room temperature, reverting to MOF A in 20 min.
ActivationHeating MOF A at 100 deg C for 5 min removes water and gives purple A-100.
Scalability contextThermal conversion of preformed crystals; no scale limitation stated.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
OtherMOF Anot statedmain p.6 · Conversion Experiments · Figure S4
Complete recipeSource: Main

Route 3: Drop Cast

main p.6 · Preparation of the MOF A Film · Figure 4

Metal precursorsfully activated ground MOF A
Linker precursorsfully activated ground MOF A
Solventsmethanol (5 mL dispersion; 0.1 mL dispensed)
Additivesnone
Atmosphereair drying followed by vacuum
Temperatureroom temperature
Time0.5 air evaporation plus 0.5 vacuum solvent removal
Substrate orientationscreen-printed gold electrode sheet; no orientation specified
Oxidant / reductantnone
Work-upUltrasonication/mixing, drop-casting, natural methanol evaporation in air for 30 min, vacuum for 30 min.
ActivationStarting MOF A fully activated before grinding; final electrode vacuumed to remove solvent.
Scalability contextDevice-scale drop-cast film made from 100 mg MOF A in 5 mL methanol.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Otherfully activated and ground MOF A100 mgmain p.6 · Preparation of the MOF A Film · Figure 4
Solventmethanol5 mL; 0.1 mL mixture droppedmain p.6 · Preparation of the MOF A Film · Figure 4
Otherscreen-printed gold electrodeone electrode sheetmain p.6 · Preparation of the MOF A Film · Figure 4
Complete recipeSource: Both

Route 4: Solvothermal

main p.6 · Experimental Section - Synthesis of MOF A

Metal precursorsCo(NO3)2.6H2O (0.015 g, 0.05 mmol)
Linker precursorsH8L calix[4]resorcinarene macrocycle (0.014 g, 0.01 mmol)
SolventsDMF/H2O mixture, 8 mL, 2:6 v/v
AdditivesHNO3 (0.05 mL, 3 M)
Atmospheresealed/thermal reaction atmosphere not specified
Temperature100
Time72
Oxidant / reductantnone stated
Work-upCooled to room temperature; obtained red crystals washed with deionised water.
Activationnone for as-grown MOF A; purity checked by PXRD.
Scalability contextYield about 70% based on H8L on 0.01 mmol linker scale.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCo(NO3)2.6H2O0.015 g, 0.05 mmolmain p.6 · Experimental Section - Synthesis of MOF A
LinkerH8L0.014 g, 0.01 mmolmain p.6 · Experimental Section - Synthesis of MOF A
SolventDMF/H2O8 mL, 2:6 v/vmain p.6 · Experimental Section - Synthesis of MOF A
AcidHNO30.05 mL · 3 Mmain p.6 · Experimental Section - Synthesis of MOF A
Partial recipeSource: Both

Route 5: Other

main p.3 and p.6 · Results and Discussion; Conversion Experiments · Figures 1 and 3

Metal precursorsMOF A Co framework
Linker precursorsMOF A calix[4]resorcinarene framework
Solventsnone added
AdditivesNO2 gas
AtmosphereNO2 gas at 298 K and 1 bar reported for adsorption study; conversion experiment says NO2 gas atmosphere
Temperature25
Time0.333 for colour change; 12 for conversion experiment/weighing uptake
Oxidant / reductantNO2 guest/electron acceptor gas
Work-upEvacuation converts conductive A-NO2 back toward A-100/A depending context; mother liquor restores red MOF A in conversion experiment.
ActivationNo separate activation beyond NO2 exposure stated for crystal conversion.
Scalability contextGas loading performed on crystals and film; exact NO2 flow/concentration for crystal bottle conversion not fully specified.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherMOF Anot stated for crystal structure; 208.4 mg for uptake testmain p.3 and p.6 · Results and Discussion; Conversion Experiments · Figures 1 and 3
AdditiveNO2 gas12 h exposure for uptake/conversion; 20 min colour change · 1 bar in adsorption studymain p.3 and p.6 · Results and Discussion; Conversion Experiments · Figures 1 and 3
Partial recipeSource: Both

Route 6: Other

main p.6 · Conversion Experiments · Figure 7b

Metal precursorsMOF A-100 Co framework
Linker precursorsMOF A-100 calix[4]resorcinarene framework
Solventsnone added
AdditivesNO2 gas
AtmosphereNO2 gas; 298 K, 1 bar in adsorption study
Temperature25
Time12
Oxidant / reductantNO2 guest/electron acceptor gas
Work-upPlaced in vacuum to turn purple (MOF A-100).
ActivationStarting material is activated A-100 from 100 deg C heating.
Scalability contextUptake test used 384.8 mg MOF A-100.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherMOF A-100384.8 mg for uptake testmain p.6 · Conversion Experiments · Figure 7b
AdditiveNO2 gas12 h exposure · 1 bar in adsorption studymain p.6 · Conversion Experiments · Figure 7b