Synthesis · Highly Effective Generation of Singlet Oxygen by an Imidazole-Linked Robust Photosensitizing Covalent Organic Framework

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: Solvothermal

S5 · Synthesis of Model Compound

Linker precursorsPyTO (25 mg, 0.09 mmol); benzaldehyde (30 uL, 0.30 mmol)

Solventsdioxane (2.0 mL)

Additivesammonium acetate (86 mg, 1.12 mmol)

Atmospheresealed under vacuum after three freeze-pump-thaw cycles

Temperature120

Time72

Work-upfiltered; washed with DMF, ethanol and THF; Soxhlet extraction with THF for 48 h

Activationdried under vacuum at 120 deg C overnight

Scalability context10 mL Schlenk tube scale; 72% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PyTO	25 mg, 0.09 mmol	S5 · Synthesis of Model Compound
Linker	benzaldehyde	30 uL, 0.30 mmol	S5 · Synthesis of Model Compound
Additive	ammonium acetate	86 mg, 1.12 mmol	S5 · Synthesis of Model Compound
Solvent	dioxane	2.0 mL	S5 · Synthesis of Model Compound

Partial recipeSource: SI

Route 2: Other

S5-S6 · Praparation of PC@PyPor-COF

Linker precursorsPyPor-COF (5.1 mg)

Solventswater

Additivescholesterol (10.3 mg); soybean phosphate (40.5 mg)

Atmosphereambient

Temperatureroom temperature

Time24

Work-upcentrifuged and washed several times to remove free cholesterol and soybean phosphate; dried

Scalability context10 mL test tube scale; exact water volume not stated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PyPor-COF	5.1 mg	S5-S6 · Praparation of PC@PyPor-COF
Additive	cholesterol	10.3 mg	S5-S6 · Praparation of PC@PyPor-COF
Additive	soybean phosphate	40.5 mg	S5-S6 · Praparation of PC@PyPor-COF
Solvent	water	Not specified	S5-S6 · Praparation of PC@PyPor-COF

Complete recipeSource: Both

Route 3: Solvothermal

21573 · Experimental Section · Table S1

Linker precursorsPyTO (12.6 mg, 0.048 mmol); p-Por-CHO (17.4 mg, 0.024 mmol)

Solventso-DCB (0.2 mL), dioxane (0.6 mL), n-BuOH (1.8 mL)

Additivesammonium acetate (22.2 mg, 0.288 mmol)

Atmospheresealed under vacuum after three freeze-pump-thaw cycles

Temperature150

Time168

Work-upcooled to room temperature; solid filtered; washed with DMF, ethanol, and THF; Soxhlet extraction with THF for 48 h

Activationpowder collected and dried under vacuum at 120 deg C overnight

Scalability context10 mL Schlenk tube scale; 92% reported yield; Table S1 shows extensive condition optimisation with only entry 25 giving high crystallinity.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PyTO	12.6 mg, 0.048 mmol	21573 · Experimental Section · Table S1
Linker	5,10,15,20-tetrakis (4-benzaldehyde) porphyrin (p-Por-CHO)	17.4 mg, 0.024 mmol	21573 · Experimental Section · Table S1
Additive	ammonium acetate	22.2 mg, 0.288 mmol	21573 · Experimental Section · Table S1
Solvent	ortho-dichlorobenzene (o-DCB)	0.2 mL	21573 · Experimental Section · Table S1
Solvent	dioxane	0.6 mL	21573 · Experimental Section · Table S1
Solvent	n-BuOH	1.8 mL	21573 · Experimental Section · Table S1

Complete recipeSource: SI

Route 4: Other

S4 · Synthesis of pyrene-4,5,9,10-tetraone (PyTO) · Scheme S1

Linker precursorspyrene (4 g, 20 mmol)

SolventsCH2Cl2 (80 mL), acetonitrile (80 mL), H2O (100 mL)

Temperature40

Timeovernight

Oxidant / reductantNaIO4 (35.0 g, 163.6 mmol); RuCl3.xH2O (0.5 g, 2.4 mmol)

Work-uprinsed with H2O (500 mL), extracted with CH2Cl2, dried at 80 deg C under reduced pressure, column chromatography with CH2Cl2 eluent

Scalability contextReported yield 45%.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	pyrene	4 g, 20 mmol	S4 · Synthesis of pyrene-4,5,9,10-tetraone (PyTO) · Scheme S1
Oxidant	NaIO4	35.0 g, 163.6 mmol	S4 · Synthesis of pyrene-4,5,9,10-tetraone (PyTO) · Scheme S1
Other	RuCl3.xH2O	0.5 g, 2.4 mmol	S4 · Synthesis of pyrene-4,5,9,10-tetraone (PyTO) · Scheme S1
Solvent	CH2Cl2	80 mL	S4 · Synthesis of pyrene-4,5,9,10-tetraone (PyTO) · Scheme S1
Solvent	acetonitrile	80 mL	S4 · Synthesis of pyrene-4,5,9,10-tetraone (PyTO) · Scheme S1
Solvent	H2O	100 mL	S4 · Synthesis of pyrene-4,5,9,10-tetraone (PyTO) · Scheme S1