Synthesis · Electrical Conductivity in a Porous, Cubic Rare-Earth Catecholate

3 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

SI p.S3 · Typical synthesis of M6HOTP2

Metal precursorsEu(NO3)3.5H2O, 9.6 mmol, 80 equiv

Linker precursorsHHTP, 0.12 mmol, 1 equiv, 54 mg

Solvents0.8 mL DMI for HHTP; 7.2 mL deionized and deoxygenated water for metal nitrate

AdditivesClean glass slide pieces; hot 1% acetic acid wash for impurity removal

AtmosphereSolutions prepared and work-up performed in N2-filled glovebox; DMI and water deoxygenated

Temperature160

Time11

Work-upMother liquor decanted; soaked in deoxygenated water, methanol and acetonitrile; Eu product additionally soaked twice in hot 80 C 1% acetic acid between the first two water soaks.

ActivationFor conductivity, crystals heated under dynamic vacuum at 95 C for 18 h.

Scalability contextInitial Eu product mixtures contained small amounts of needle-shaped unwanted phases that were removed by acid washing.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Eu(NO3)3.5H2O	9.6 mmol; 80 equiv	SI p.S3 · Typical synthesis of M6HOTP2
Linker	Hexahydroxytriphenylene (HHTP)	0.12 mmol; 1 equiv; 54 mg	SI p.S3 · Typical synthesis of M6HOTP2
Solvent	N,N'-dimethylimidazolidinone (DMI)	0.8 mL · deoxygenated by bubbling with N2 for 24 h	SI p.S3 · Typical synthesis of M6HOTP2
Solvent	Deionized and deoxygenated water	7.2 mL	SI p.S3 · Typical synthesis of M6HOTP2
Acid	Acetic acid	hot 80 C 1% acetic acid; two soaks · 1%	SI p.S3 · Typical synthesis of M6HOTP2

Complete recipeSource: Both

Route 2: Solvothermal

SI p.S4 · Typical synthesis of M6HOTP2

Metal precursorsLa(NO3)3.6H2O, 9.6 mmol, 80 equiv

Linker precursorsHHTP, 0.12 mmol, 1 equiv, 54 mg

Solvents0.8 mL DMI for HHTP; 7.2 mL deionized and deoxygenated water for metal nitrate

AdditivesClean glass slide pieces added as crystallisation surface

AtmosphereSolutions prepared and work-up performed in N2-filled glovebox; DMI and water deoxygenated

Temperature160

Time11

Work-upGeneral water/methanol/acetonitrile soaking work-up attempted.

Scalability contextBulk product mixtures were significantly contaminated and the desired phase could not be isolated for studies beyond single-crystal XRD.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	La(NO3)3.6H2O	9.6 mmol; 80 equiv	SI p.S4 · Typical synthesis of M6HOTP2
Linker	Hexahydroxytriphenylene (HHTP)	0.12 mmol; 1 equiv; 54 mg	SI p.S4 · Typical synthesis of M6HOTP2
Solvent	N,N'-dimethylimidazolidinone (DMI)	0.8 mL · deoxygenated by bubbling with N2 for 24 h	SI p.S4 · Typical synthesis of M6HOTP2
Solvent	Deionized and deoxygenated water	7.2 mL	SI p.S4 · Typical synthesis of M6HOTP2

Complete recipeSource: Both

Route 3: Solvothermal

SI p.S3 · Typical synthesis of M6HOTP2

Metal precursorsY(NO3)3.6H2O, 9.6 mmol, 80 equiv

Linker precursorsHHTP, 0.12 mmol, 1 equiv, 54 mg

Solvents0.8 mL DMI for HHTP; 7.2 mL deionized and deoxygenated water for metal nitrate

AdditivesClean glass slide pieces added as crystallisation surface

AtmosphereSolutions prepared and work-up performed in N2-filled glovebox; DMI and water deoxygenated

Temperature160

Time11

Work-upMother liquor decanted in glovebox; powder soaked 5 times for 3-24 h in deoxygenated water, then 5 times in methanol, then 5 times in acetonitrile.

ActivationFor conductivity, crystals heated under dynamic vacuum at 95 C for 18 h; for N2 adsorption, heated to 90 C under dynamic vacuum until outgas rate <2 mTorr/min.

Scalability contextReaction performed in a 23 mL PTFE-lined stainless-steel autoclave; extending reaction time increased crystal size but caused colourless impurity.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Y(NO3)3.6H2O	9.6 mmol; 80 equiv	SI p.S3 · Typical synthesis of M6HOTP2
Linker	Hexahydroxytriphenylene (HHTP)	0.12 mmol; 1 equiv; 54 mg	SI p.S3 · Typical synthesis of M6HOTP2
Solvent	N,N'-dimethylimidazolidinone (DMI)	0.8 mL · deoxygenated by bubbling with N2 for 24 h	SI p.S3 · Typical synthesis of M6HOTP2
Solvent	Deionized and deoxygenated water	7.2 mL	SI p.S3 · Typical synthesis of M6HOTP2
Additive	Clean glass slide pieces	Not specified	SI p.S3 · Typical synthesis of M6HOTP2