Synthesis · Fluorescent metal-organic frameworks for selective sensing of toxic cations (Tl3+, Hg2+) and highly oxidizing anions ((CrO4)2−, (Cr2O7)2−, (MnO4)−)

Partial recipeSource: SI

Route 1: Other

SI pp.28-29 · Synthesis of linker · Figures S26-S28

Linker precursors1,2-phenylenediamine; 2,1,3-benzothiadiazole; 4,7-dibromo-2,1,3-benzothiadiazole; dimethyl 4,4'-(benzothiadiazole-4,7-diyl)dibenzoate

SolventsCH2Cl2; HBr; 1,4-dioxane; MeOH/THF/H2O

Additivestriethylamine; thionyl chloride; Br2; saturated NaHSO3; 4-(methoxycarbonyl)benzeneboronic acid; K2CO3; Pd(PPh3)4; KOH; HCl

AtmosphereN2 for Suzuki coupling step; otherwise not specified

Temperatureroom temperature, 60, 85, 110, 80

Time0.25, 6, 6, 72, 12

Oxidant / reductantBr2 bromination; NaHSO3 quench; thionyl chloride cyclisation reagent

Work-upRotary evaporation, water/HCl acidification to pH 1 for benzothiadiazole extraction; filtration/water/cold diethyl ether washing for dibromo intermediate; filtration and rotary evaporation after Suzuki step followed by silica chromatography; final acidification to pH 2, filtration, water wash and vacuum drying.

Activationfinal linker dried under vacuum

Scalability contextReported intermediate yields: 2,1,3-benzothiadiazole 1.16 g (92%); 4,7-dibromo intermediate 2.01 g (94%); dimethyl ester 1.98 g (72%); final acid linker 0.92 g (98%).

Show 16 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	1,2-phenylenediamine	1.0 g, 9.25 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Solvent	CH2Cl2	30 mL	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Base	triethylamine	3.74 g, 37.0 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Other	thionyl chloride	1.35 mL, 18.49 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Other	2,1,3-benzothiadiazole	1 g, 7.34 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Acid	HBr	15 mL plus 20 mL · 48%	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Oxidant	Br2	3.52 g, 22.03 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Reductant	NaHSO3	100 mL saturated solution · saturated	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Solvent	1,4-dioxane	160 mL	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Other	4,7-dibromo-2,1,3-benzothiadiazole	2 g, 6.8 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Other	4-(methoxycarbonyl) benzeneboronic acid	2.57 g, 14.3 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Base	anhydrous K2CO3	5.62 g, 40.8 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Additive	Pd(PPh3)4	0.79 g, 0.68 mmol	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Solvent	MeOH/THF/H2O	20 mL / 20 mL / 10 mL	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Base	KOH	g, mmol not reported in text layer	SI pp.28-29 · Synthesis of linker · Figures S26-S28
Acid	concentrated HCl	dropwise to pH 2 · concentrated	SI pp.28-29 · Synthesis of linker · Figures S26-S28

Complete recipeSource: Main

Route 2: Solvothermal

p009 / article p.1161 · Synthesis of [Mn4(C20H10N2O4S)2(HCOO)4(DEF)2]

Metal precursorsMnCl2.4H2O (79 mg, 0.398 mmol)

Linker precursors4,4'-(benzothiadiazole-4,7-diyl)dibenzoic acid (50 mg, 0.133 mmol)

SolventsN,N'-diethylformamide (7 mL)

Atmospherenot specified

Temperature150

Time72

Work-upFiltered, washed with N,N-diethylformamide and methanol, and dried under vacuum.

Activationdried under vacuum

Scalability context14 mL Teflon-lined autoclave batch; yield 79.6 mg (44.3%).

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	MnCl2.4 H2O	79 mg, 0.398 mmol	p009 / article p.1161 · Synthesis of [Mn4(C20H10N2O4S)2(HCOO)4(DEF)2]
Linker	4,4'-(benzothiadiazole-4,7-diyl)dibenzoic acid	50 mg, 0.133 mmol	p009 / article p.1161 · Synthesis of [Mn4(C20H10N2O4S)2(HCOO)4(DEF)2]
Solvent	N,N'-diethylformamide	7 mL	p009 / article p.1161 · Synthesis of [Mn4(C20H10N2O4S)2(HCOO)4(DEF)2]

Complete recipeSource: Main

Route 3: Solvothermal

p009 / article p.1161 · Synthesis of [Pb(C20H10N2O4S)(DMF)]

Metal precursorsPbCl2 (74 mg, 0.266 mmol)

Linker precursors4,4'-(benzothiadiazole-4,7-diyl)dibenzoic acid (50 mg, 0.133 mmol)

SolventsN,N-dimethylformamide (7 mL)

AdditivesHClO4 (20 uL; visually verified from rendered page because the text layer misread the micro symbol)

Atmospherenot specified

Temperature150

Time72

Work-upFiltered, washed with N,N'-dimethylformamide and methanol, and dried under vacuum.

Activationdried under vacuum

Scalability context14 mL Teflon-lined autoclave batch; yield 34.26 mg (39.35%).

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	PbCl2	74 mg, 0.266 mmol	p009 / article p.1161 · Synthesis of [Pb(C20H10N2O4S)(DMF)]
Linker	4,4'-(benzothiadiazole-4,7-diyl)dibenzoic acid	50 mg, 0.133 mmol	p009 / article p.1161 · Synthesis of [Pb(C20H10N2O4S)(DMF)]
Solvent	N,N-dimethylformamide	7 mL	p009 / article p.1161 · Synthesis of [Pb(C20H10N2O4S)(DMF)]
Acid	HClO4	20 uL	p009 / article p.1161 · Synthesis of [Pb(C20H10N2O4S)(DMF)]

Fluorescent metal-organic frameworks for selective sensing of toxic cations (Tl3+, Hg2+) and highly oxidizing anions ((CrO4)2−, (Cr2O7)2−, (MnO4)−)

3 structured synthesis routes