Synthesis · A stable porphyrinic metal-organic framework pore-functionalized by high-density carboxylic groups for proton conduction

5 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

S6 · Synthesis of [Co(DCDPP)].5H2O (BUT-83)

Metal precursorsCo(NO3)2.6H2O

Linker precursorsH2DCDPP

SolventsN,N'-dimethylformamide (DMF)

Additivestetrafluoroboric acid aqueous solution as competing reagent

Atmospheresealed 20 mL Pyrex vial

Temperature80

Time72

Work-upAfter cooling to room temperature, deep purple crystals were harvested by filtration, washed with DMF and acetone, and dried in air; yield 28 mg.

ActivationFor adsorption: soak as-synthesised BUT-83 in fresh DMF for 24 h, discard extract; add fresh acetone for 8 h, repeat three times over one day; remove acetone; dry under dynamic vacuum <10^-3 Torr at room temperature for 3 h; outgas 10 h at 70 deg C. For proton conductivity: further dried 10 h at 80 deg C.

Scalability contextSmall-vial solvothermal synthesis with milligram quantities; no scale-up or continuous synthesis demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	20 mg, 0.07 mmol	S6 · Synthesis of [Co(DCDPP)].5H2O (BUT-83)
Linker	H2DCDPP	30 mg, 0.04 mmol	S6 · Synthesis of [Co(DCDPP)].5H2O (BUT-83)
Acid	tetrafluoroboric acid aqueous solution	1.5 mL · 48%	S6 · Synthesis of [Co(DCDPP)].5H2O (BUT-83)
Solvent	N,N'-dimethylformamide (DMF)	10 mL	S6 · Synthesis of [Co(DCDPP)].5H2O (BUT-83)
Solvent	DMF	wash and 24 h soak for activation	S6 · Synthesis of [Co(DCDPP)].5H2O (BUT-83)
Solvent	acetone	wash and three 8 h exchanges	S6 · Synthesis of [Co(DCDPP)].5H2O (BUT-83)

Vague recipeSource: SI

Route 2: Unknown

S6 · Synthesis of Co(DpyDtolP) · Fig. S7

Linker precursorsDpyDtolP ligand

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Linker	DpyDtolP	Not specified	S6 · Synthesis of Co(DpyDtolP) · Fig. S7

Complete recipeSource: SI

Route 3: Other

S4 · Synthesis, step (a) · Scheme 1

Linker precursors4-pyridinecarboxaldehyde; pyrrole

Solventsethyl acetate/petroleum ether for recrystallisation; dichloromethane/ethyl acetate for chromatography

Atmospherenitrogen atmosphere

Temperature85

Time8

Work-upReaction mixture dried by evaporation; chromatographed on silica in dichloromethane/ethyl acetate from 100/0 to 90/10; recrystallised in ethyl acetate/petroleum ether to give 3.557 g pale yellow crystals, 65.4% yield.

Scalability contextMillimole-scale ligand precursor synthesis; no scale-up study reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	4-pyridinecarboxaldehyde	3.0 mL, 31.9 mmol	S4 · Synthesis, step (a) · Scheme 1
Linker	pyrrole	20.00 mL, 0.29 mol	S4 · Synthesis, step (a) · Scheme 1
Solvent	dichloromethane/ethyl acetate	chromatography gradient 100/0 to 90/10	S4 · Synthesis, step (a) · Scheme 1
Solvent	ethyl acetate/petroleum ether	recrystallisation solvent	S4 · Synthesis, step (a) · Scheme 1

Complete recipeSource: SI

Route 4: Other

S5 · Synthesis, step (b) · Scheme 1

Linker precursors5-(4-pyridyl)dipyrromethane; methyl 4-formylbenzoate

Solventsanhydrous dichloromethane; trichloromethane/ethanol for chromatography; trichloromethane/hexane for recrystallisation

Additivestrifluoroacetic acid

Atmospherenitrogen atmosphere

Temperatureice bath then room temperature

Timeabout 0.33 h before DDQ addition plus 3 h after DDQ addition

Oxidant / reductant2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)

Work-upOrganic phase washed with saturated aqueous NaHCO3 and dried over anhydrous Na2SO4; purified by silica chromatography in trichloromethane/ethanol from 100/0 to 98/2; recrystallised in trichloromethane/hexane to give 533 mg purple product, 32.4% yield.

Scalability contextSub-gram porphyrin intermediate synthesis; no scale-up study reported.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	5-(4-Pyridyl)dipyrromethane	1.000 g, 4.48 mmol	S5 · Synthesis, step (b) · Scheme 1
Linker	methyl 4-formylbenzoate	0.730 g, 4.48 mmol	S5 · Synthesis, step (b) · Scheme 1
Solvent	anhydrous dichloromethane (DCM)	600 mL	S5 · Synthesis, step (b) · Scheme 1
Acid	trifluoroacetic acid (TFA)	12 mL, 172.0 mmol	S5 · Synthesis, step (b) · Scheme 1
Oxidant	2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)	2.030 g, 8.96 mmol	S5 · Synthesis, step (b) · Scheme 1
Other	saturated aqueous NaHCO3	wash	S5 · Synthesis, step (b) · Scheme 1
Other	anhydrous Na2SO4	drying agent	S5 · Synthesis, step (b) · Scheme 1

Complete recipeSource: SI

Route 5: Other

S5-S6 · Synthesis, step (c) · Scheme 1

Linker precursorsH2DCOOMeDPP

Solventstetrahydrofuran/methanol mixture; chloroform extraction; water wash

Additives40% KOH solution; concentrated HCl aqueous solution

Temperature80

Time1

Work-upAfter cooling, acidified with concentrated HCl aqueous solution to pH = 3, water added, extracted with chloroform (100 mL x 3), combined organic phase washed with water three times, dried over anhydrous Na2SO4, filtered, solvent removed.

Scalability context500 mg ester precursor scale; no scale-up study reported.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H2DCOOMeDPP	500 mg, 0.126 mmol	S5-S6 · Synthesis, step (c) · Scheme 1
Solvent	tetrahydrofuran/methanol mixture	50 mL	S5-S6 · Synthesis, step (c) · Scheme 1
Base	KOH solution	20 mL · 40% w/v	S5-S6 · Synthesis, step (c) · Scheme 1
Acid	concentrated HCl aqueous solution	to pH = 3	S5-S6 · Synthesis, step (c) · Scheme 1
Solvent	water	100 mL added; 100 mL x 3 wash	S5-S6 · Synthesis, step (c) · Scheme 1
Solvent	chloroform	100 mL x 3 extraction	S5-S6 · Synthesis, step (c) · Scheme 1
Other	anhydrous Na2SO4	drying agent	S5-S6 · Synthesis, step (c) · Scheme 1