Synthesis · Lowering Band Gap of an Electroactive Metal-Organic Framework via Complementary Guest Intercalation

3 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

S-3 / render p003 · DSNDI Ligand

Linker precursors1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA); 4-aminosalicylic acid

SolventsDMF (12 mL)

AdditivesMe3SiCl (6.4 mL, 50 mmol)

AtmosphereNot specified

Temperature150

Time14

Work-upCool to room temperature; filter precipitate; wash with EtOAc, 1 M aqueous NaOH, H2O, and MeOH; yellow solid obtained.

Scalability contextReported isolated ligand yield was 0.27 g, 5%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	NDA	2.68 g, 10 mmol	S-3 / render p003 · DSNDI Ligand
Linker	4-aminosalicylic acid	4.6 g, 30 mmol	S-3 / render p003 · DSNDI Ligand
Additive	Me3SiCl	6.4 mL, 50 mmol	S-3 / render p003 · DSNDI Ligand
Solvent	DMF	12 mL	S-3 / render p003 · DSNDI Ligand

Complete recipeSource: Both

Route 2: Solvothermal

S-3 / render p003 · DSNDI-based MOF-74

Metal precursorsZn(NO3)2.6H2O (21 mg, 0.07 mmol)

Linker precursorsDSNDI ligand (17 mg, 0.03 mmol)

SolventsDMF/EtOH/H2O (3:0.5:0.5 mL)

Atmosphere20 mL sealed scintillation vial; gas atmosphere not otherwise specified

Temperature90

Time24

Work-upSonicate 5 min; heat; cool gradually; decant solvent; soak in fresh DMF (10 mL) for 5 h, repeated three times per day for 3 days; repeat same washing protocol with MeOH.

ActivationRemove trapped solvent under dynamic vacuum initially at room temperature, then heat at 80 °C for 24 h. For N2 sorption, MeOH-exchanged powder was further activated under high vacuum then at 100 °C for 24 h until outgas rate was <5 umHg/min.

Scalability contextYield reported as 76% based on DSNDI ligand.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	21 mg, 0.07 mmol	S-3 / render p003 · DSNDI-based MOF-74
Linker	DSNDI ligand	17 mg, 0.03 mmol	S-3 / render p003 · DSNDI-based MOF-74
Solvent	DMF	3 mL	S-3 / render p003 · DSNDI-based MOF-74
Solvent	EtOH	0.5 mL	S-3 / render p003 · DSNDI-based MOF-74
Solvent	H2O	0.5 mL	S-3 / render p003 · DSNDI-based MOF-74

Complete recipeSource: Both

Route 3: Other

S-3 / render p003 · TTF-doped MOF-74

Metal precursorsActivated DSNDI-based MOF-74 framework contains Zn(II) nodes

Linker precursorsActivated DSNDI-based MOF-74

SolventsMeOH

AdditivesTTF guest

AtmosphereKept in the dark; atmosphere not otherwise specified

Temperatureroom temperature not explicitly stated

Time48

Oxidant / reductantTTF acts as electron-rich donor guest after intercalation

Work-upDecant solvent; wash solid with MeOH to remove excess non-entrapped TTF.

ActivationDry under vacuum for 16 h.

Scalability contextSmall-batch postsynthetic infiltration: 15 mg activated MOF in 3 mL guest solution.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated DSNDI-based MOF-74	15 mg	S-3 / render p003 · TTF-doped MOF-74
Additive	TTF	20 mM	S-3 / render p003 · TTF-doped MOF-74
Solvent	MeOH	3 mL	S-3 / render p003 · TTF-doped MOF-74