Synthesis · De Novo Design and Facile Synthesis of Highly Crystalline 2D Conductive Metal-Organic Frameworks: A “Rotor-Stator” Strategy

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: Solvothermal

S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S2

Metal precursorscopper nitrate trihydrate

Linker precursors8OH-DCB ligand

SolventsDMAc/water, 1.0 mL/4.0 mL

Atmospherenot specified

Temperature85

Time72

Work-upAfter cooling, precipitate filtered and thoroughly washed with DMAc, EtOH and DCM.

ActivationDried under vacuum.

Scalability context10 mL Pyrex tube; SI yield 12.2 mg, 93%; main text describes high yield of 90%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	8OH-DCB ligand	10.8 mg, 0.02 mmol	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S2
Metal Source	copper nitrate trihydrate	14.5 mg, 0.06 mmol	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S2
Solvent	DMAc	1.0 mL	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S2
Solvent	water	4.0 mL	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S2

Complete recipeSource: SI

Route 2: Solvothermal

S11 · Section 2.2 Synthesis of Cu-MOFs · Scheme S4

Metal precursorscopper nitrate trihydrate

Linker precursors8OH-DCBBT ligand

SolventsDMAc/water, 1.5 mL/3.5 mL

Atmospherenot specified

Temperature85

Time72

Work-upAfter cooling, precipitate filtered and thoroughly washed with DMAc, EtOH and DCM.

ActivationDried under vacuum.

Scalability context10 mL Pyrex tube; yield 13.5 mg, 88%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	8OH-DCBBT ligand	13.0 mg, 0.02 mmol	S11 · Section 2.2 Synthesis of Cu-MOFs · Scheme S4
Metal Source	copper nitrate trihydrate	14.5 mg, 0.06 mmol	S11 · Section 2.2 Synthesis of Cu-MOFs · Scheme S4
Solvent	DMAc	1.5 mL	S11 · Section 2.2 Synthesis of Cu-MOFs · Scheme S4
Solvent	water	3.5 mL	S11 · Section 2.2 Synthesis of Cu-MOFs · Scheme S4

Complete recipeSource: SI

Route 3: Solvothermal

S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S3

Metal precursorscopper nitrate trihydrate

Linker precursors8OH-DCBT ligand

SolventsDMAc/water, 0.5 mL/4.5 mL

Atmospherenot specified

Temperature85

Time72

Work-upAfter cooling, precipitate filtered and thoroughly washed with DMAc, EtOH and DCM.

ActivationDried under vacuum.

Scalability context10 mL Pyrex tube; yield 12.3 mg, 86%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	8OH-DCBT ligand	12.0 mg, 0.02 mmol	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S3
Metal Source	copper nitrate trihydrate	14.5 mg, 0.06 mmol	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S3
Solvent	DMAc	0.5 mL	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S3
Solvent	water	4.5 mL	S10 · Section 2.2 Synthesis of Cu-MOFs · Scheme S3

Complete recipeSource: SI

Route 4: Other

S7 · Section 2.1 Synthesis of Ligands · Scheme S1

Linker precursorsCompound 2, 1,4-bis(2,3,6,7-tetramethoxy-9H-carbazol-9-yl)benzene

Solvents100 mL DCM; ice water quench

AdditivesBBr3, 1.5 mL, 15.0 mmol

Atmospherenitrogen

Temperature0 degC addition, then room temperature

Time24

Oxidant / reductantBBr3 demethylation reagent

Work-upReaction mixture poured into ice water; solid collected by filtration and washed with water.

Scalability contextGram-scale linker precursor: 1.0 g compound 2 gave 0.74 g 8OH-DCB.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Compound 2	1.0 g, 1.5 mmol	S7 · Section 2.1 Synthesis of Ligands · Scheme S1
Solvent	DCM	100 mL	S7 · Section 2.1 Synthesis of Ligands · Scheme S1
Additive	BBr3	1.5 mL, 15.0 mmol	S7 · Section 2.1 Synthesis of Ligands · Scheme S1

Complete recipeSource: SI

Route 5: Other

S9 · Section 2.1 Synthesis of Ligands · Scheme S1

Linker precursorsCompound 4, 4,7-bis(2,3,6,7-tetramethoxy-9H-carbazol-9-yl)benzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole)

Solvents100 mL DCM; ice water quench

AdditivesBBr3, 1.5 mL, 15.0 mmol

Atmospherenitrogen

Temperature0 degC addition, then room temperature

Time24

Oxidant / reductantBBr3 demethylation reagent

Work-upReaction mixture poured into ice water; solid collected by filtration and washed with water.

Scalability context1.0 g compound 4 gave 0.80 g 8OH-DCBBT.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Compound 4	1.0 g, 1.3 mmol	S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Solvent	DCM	100 mL	S9 · Section 2.1 Synthesis of Ligands · Scheme S1
Additive	BBr3	1.5 mL, 15.0 mmol	S9 · Section 2.1 Synthesis of Ligands · Scheme S1

Complete recipeSource: SI

Route 6: Other

S8 · Section 2.1 Synthesis of Ligands · Scheme S1

Linker precursorsCompound 3, 4,7-bis(2,3,6,7-tetramethoxy-9H-carbazol-9-yl)benzo[c][1,2,5]thiadiazole

Solvents100 mL DCM; ice water quench

AdditivesBBr3, 1.5 mL, 15.0 mmol

Atmospherenitrogen

Temperature0 degC addition, then room temperature

Time24

Oxidant / reductantBBr3 demethylation reagent

Work-upReaction mixture poured into ice water; solid collected by filtration and washed with water.

Scalability context1.0 g compound 3 gave 0.79 g 8OH-DCBT.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Compound 3	1.0 g, 1.4 mmol	S8 · Section 2.1 Synthesis of Ligands · Scheme S1
Solvent	DCM	100 mL	S8 · Section 2.1 Synthesis of Ligands · Scheme S1
Additive	BBr3	1.5 mL, 15.0 mmol	S8 · Section 2.1 Synthesis of Ligands · Scheme S1