Synthesis · In Situ Construction of Amide-Functionalized 2D Conjugated Metal-Organic Frameworks with Multiple Active Sites for High-Performance Potassium-Ion Batteries

4 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

S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1

Metal precursorsnone

Linker precursors4,5-dimethoxy-1,2-benzenediamine; 2,4,5-trimethoxybenzoic acid; compound 1 intermediate

Solventschloroform; DCM; water; chloroform/toluene for crystals

AdditivesPh3PCl2; HCl; NaHCO3; MgSO4; BBr3

Atmospherenitrogen during BBr3 demethylation

Temperaturereflux for amidation; 0 C addition then room temperature for demethylation

Time17 h amidation; 12 h demethylation

Oxidant / reductantBBr3 demethylation reagent

Work-uppoured into ice-cold water, extracted with DCM, acid/base washes, brine, dried over MgSO4, silica gel column; demethylation poured into ice water, filtered, washed with water

Activationnone reported for ligand

Scalability contextStep yields: 93% for compound 1 and 94% for 6OH-HBB; main text states 93% over two steps, which is inconsistent with SI step yields.

Show 9 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	Ph3PCl2	1.60 g, 4.8 mmol	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Linker	4,5-dimethoxy-1,2-benzenediamine	0.17 g, 1.0 mmol	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Linker	2,4,5-trimethoxybenzoic acid	0.51 g, 2.4 mmol	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Solvent	chloroform	40 mL	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Other	compound 1	1.1 g, 2.0 mmol	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Solvent	DCM	100 mL	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Other	BBr3	0.9 mL, 9 mmol · 99%	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Acid	HCl	4 M aqueous solution	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Base	NaHCO3	saturated aqueous solution	S8-S9 · Section 2.1 Synthesis of Ligands · Scheme S1

Partial recipeSource: SI

Route 2: Unknown

S9 · Section 2.1 Synthesis of Ligands · Scheme S1

Metal precursorsnone

Linker precursorsnot specified in this paper

Solventsnot specified in this paper

Additivesnot specified in this paper

Atmospherenot specified in this paper

Work-upnot specified in this paper

Scalability contextPrepared according to prior reported procedures; not fetched per instruction.

Complete recipeSource: Both

Route 3: Solvothermal

S9-S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S2

Metal precursorscopper acetate monohydrate (27.9 mg, 0.14 mmol)

Linker precursors6OH-HBB ligand (17.8 mg, 0.04 mmol)

SolventsDMF/water 2 mL/2 mL

Additivespotassium acetate (49.1 mg, 0.50 mmol)

Atmospherenot specified for MOF Pyrex-tube heating

Temperature85

Time72

Oxidant / reductantnone stated

Work-upcooled; precipitate filtered; washed thoroughly with DMF, EtOH and DCM; dried under vacuum

Activationdried under vacuum; porosity samples degassed at 80 C for 12 h under vacuum (10^-5 bar) before N2 sorption

Scalability context10 mL Pyrex tube; isolated black powder 21.0 mg, 88% yield.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	6OH-HBB ligand	17.8 mg, 0.04 mmol	S9-S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S2
Additive	potassium acetate	49.1 mg, 0.50 mmol	S9-S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S2
Metal Source	copper acetate monohydrate	27.9 mg, 0.14 mmol	S9-S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S2
Solvent	DMF	2 mL	S9-S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S2
Solvent	water	2 mL	S9-S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S2

Complete recipeSource: Both

Route 4: Solvothermal

S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S3

Metal precursorscopper acetate monohydrate (27.9 mg, 0.14 mmol)

Linker precursors6OH-Salphen ligand (16.6 mg, 0.04 mmol)

SolventsDMF/water 2.5 mL/3.5 mL

Additivesnone stated

Atmospherenot specified

Temperature85

Time72

Oxidant / reductantnone stated

Work-upcooled; precipitate collected by filtration; washed thoroughly with DMF, EtOH and DCM; dried under vacuum

Activationdried under vacuum; porosity samples degassed at 80 C for 12 h under vacuum (10^-5 bar) before N2 sorption

Scalability context10 mL Pyrex tube; isolated black powder 23.2 mg, 92% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	6OH-Salphen ligand	16.6 mg, 0.04 mmol	S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S3
Metal Source	copper acetate monohydrate	27.9 mg, 0.14 mmol	S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S3
Solvent	DMF	2.5 mL	S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S3
Solvent	water	3.5 mL	S10 · Section 2.2 Synthesis of 2D c-MOFs · Scheme S3