Synthesis · Pd uptake and H2S sensing by an amphoteric metal-organic framework with a soft core and rigid side arms

10 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

SI p.S6-S7 · Crystallization of BFMOF-1

Metal precursorsPb(NO3)2

Linker precursorsBackfolded linker L

SolventsWater and N,N-dimethylacetamide (DMA), 1.5 mL, 1:3 v/v

AtmosphereFlame-sealed heavy-wall glass tube; internal atmosphere not otherwise specified.

Temperature100

Time48

Work-upSlow cooling at 0.1 C/min to room temperature; isolated single crystals.

Scalability contextSmall sealed-tube batch: 5.2 mg crystals, 56% yield based on L.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	L	7.2 mg, 6.0 micromol	SI p.S6-S7 · Crystallization of BFMOF-1
Metal Source	Pb(NO3)2	6.0 mg, 18.0 micromol	SI p.S6-S7 · Crystallization of BFMOF-1
Solvent	water	part of 1.5 mL mixture · 1:3 water:DMA v/v	SI p.S6-S7 · Crystallization of BFMOF-1
Solvent	N,N-dimethylacetamide	part of 1.5 mL mixture · 1:3 water:DMA v/v	SI p.S6-S7 · Crystallization of BFMOF-1

Complete recipeSource: Both

Route 2: Other

SI p.S7 · Transformation of BFMOF-1 into BFMOF-1a

SolventsEthanol (5 mL); alternatively CH3CN or CH2Cl2

AtmosphereRoom-temperature solvent immersion; exposure to air noted in main text.

Temperatureroom temperature

Time0.5

Work-upSolvent immersion transforms crystals to BFMOF-1a; isolation details not specified beyond product analysis.

ActivationDesolvation/solvent exchange removes DMA and water guests.

Scalability contextReported for a 30 mg crystal sample.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BFMOF-1 crystal sample	30 mg	SI p.S7 · Transformation of BFMOF-1 into BFMOF-1a
Solvent	ethanol	5 mL	SI p.S7 · Transformation of BFMOF-1 into BFMOF-1a
Solvent	CH3CN or CH2Cl2	alternative solvents	SI p.S7 · Transformation of BFMOF-1 into BFMOF-1a

Complete recipeSource: SI

Route 3: Other

SI p.S8 · Treatment of BFMOF-1a by AgBF4

Metal precursorsAgBF4

SolventsToluene

AtmosphereRoom temperature, atmosphere not specified.

Temperatureroom temperature

Time12

Work-upSeparated by centrifugation and washed with toluene (3 mL x 5).

Scalability context3.0 mg host sample.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BFMOF-1a	3.0 mg	SI p.S8 · Treatment of BFMOF-1a by AgBF4
Metal Source	AgBF4	2.0 mL solution · 0.29% w/w in toluene	SI p.S8 · Treatment of BFMOF-1a by AgBF4
Solvent	toluene	2.0 mL plus washes 3 mL x 5	SI p.S8 · Treatment of BFMOF-1a by AgBF4

Complete recipeSource: SI

Route 4: Other

SI p.S8 · 1a-H2S from treatment of BFMOF-1a with H2S gas

AdditivesH2S gas

AtmosphereH2S

Temperatureroom temperature

Time0.5

Oxidant / reductantH2S electron donor/Lewis base guest.

Work-upNot specified.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BFMOF-1a	Not specified	SI p.S8 · 1a-H2S from treatment of BFMOF-1a with H2S gas
Other	H2S gas	Not specified	SI p.S8 · 1a-H2S from treatment of BFMOF-1a with H2S gas

Complete recipeSource: SI

Route 5: Other

SI p.S8-S9 · Treatment of BFMOF-1a by HgCl2/Pt(CH3CN)2Cl2/CdCl2

Metal precursorsHgCl2, Pt(CH3CN)2Cl2 or CdCl2

SolventsCH2Cl2 for HgCl2 and Pt(CH3CN)2Cl2; 1:1 CH2Cl2/ethanol for CdCl2

AtmosphereRoom temperature, atmosphere not specified.

Temperatureroom temperature

Time12

Work-upSeparated by centrifugation; washed by dichloromethane or ethanol (3 mL x 5).

Scalability contextEach uses 3.0 mg BFMOF-1a.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BFMOF-1a	3.0 mg	SI p.S8-S9 · Treatment of BFMOF-1a by HgCl2/Pt(CH3CN)2Cl2/CdCl2
Metal Source	HgCl2	2.0 mL solution · 0.25% w/w in dichloromethane	SI p.S8-S9 · Treatment of BFMOF-1a by HgCl2/Pt(CH3CN)2Cl2/CdCl2
Metal Source	Pt(CH3CN)2Cl2	2.0 mL solution · 0.25% w/w in dichloromethane	SI p.S8-S9 · Treatment of BFMOF-1a by HgCl2/Pt(CH3CN)2Cl2/CdCl2
Metal Source	CdCl2	2.0 mL solution · 0.25% w/w in 1:1 dichloromethane/ethanol	SI p.S8-S9 · Treatment of BFMOF-1a by HgCl2/Pt(CH3CN)2Cl2/CdCl2

Partial recipeSource: SI

Route 6: Other

SI p.S11 · Figure S5 caption · Figure S5

Metal precursorsEmbedded PdCl2 in 1a-PdCl2

AdditivesH2 atmosphere

AtmosphereH2

Temperatureroom temperature

Time3

Oxidant / reductantH2 reductant, reducing embedded Pd(II) to Pd(0).

Work-upNot specified.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	1a-PdCl2	Not specified	SI p.S11 · Figure S5 caption · Figure S5
Reductant	H2	atmosphere	SI p.S11 · Figure S5 caption · Figure S5

Complete recipeSource: SI

Route 7: Other

SI p.S7-S8 · 1a-PdCl2 from treatment of BFMOF-1a with Pd(CH3CN)2Cl2

Metal precursorsPd(CH3CN)2Cl2

SolventsDichloromethane

AtmosphereRoom temperature, atmosphere not specified.

Temperatureroom temperature

Time12

Work-upSeparated by centrifugation and washed with dichloromethane (5 x 3 mL).

Scalability context3.0 mg host sample.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BFMOF-1a	3.0 mg	SI p.S7-S8 · 1a-PdCl2 from treatment of BFMOF-1a with Pd(CH3CN)2Cl2
Metal Source	Pd(CH3CN)2Cl2	2.0 mL solution · 0.24% w/w, saturated dichloromethane solution	SI p.S7-S8 · 1a-PdCl2 from treatment of BFMOF-1a with Pd(CH3CN)2Cl2
Solvent	dichloromethane	2.0 mL plus washes 5 x 3 mL	SI p.S7-S8 · 1a-PdCl2 from treatment of BFMOF-1a with Pd(CH3CN)2Cl2

Partial recipeSource: Both

Route 8: Other

SI p.S10 · Figure S3 caption · Figure S3

SolventsDMA

AtmosphereNot specified

Temperature120

Time12

Work-upNot specified.

ActivationDMA treatment regenerates parent-like BFMOF-1 prime phase.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BFMOF-1a	Not specified	SI p.S10 · Figure S3 caption · Figure S3
Solvent	DMA	Not specified	SI p.S10 · Figure S3 caption · Figure S3

Complete recipeSource: SI

Route 9: Other

SI p.S8 · Detection of H2S · Figure 4

SolventsWater

AdditivesNaSH solutions used as H2S source

AtmosphereSealed/closed vials not specified; heated at 80 C.

Temperature80

Time0.5

Oxidant / reductantNaSH/H2S analyte.

Work-upPhotographed after treatment.

Scalability context6.0 mg BFMOF-1 divided into six 15 mL vials.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BFMOF-1 crystal sample	6.0 mg	SI p.S8 · Detection of H2S · Figure 4
Other	NaSH solutions	10 mL per vial · 0, 1, 2, 5, 20, 100 ppm NaSH; Figure 4 reports 0, 0.6, 1.2, 3.0, 12, 60 ppm H2S	SI p.S8 · Detection of H2S · Figure 4

Complete recipeSource: SI

Route 10: Other

SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1

Metal precursorsPd(PPh3)2Cl2 and CuI catalysts for Sonogashira steps; no framework metal in linker synthesis.

Linker precursors4-bromothioanisole; methyl 4-hydroxybenzoate; pentaerythritol tetrabromide; intermediate C1; intermediate C2; intermediate C3.

SolventsTriethylamine; methanol; DMF; CHCl3; THF; dichloromethane; hexane/ethyl acetate chromatography eluents; water.

AdditivesPPh3, K2CO3, Br2, NaSO3, KOH, HCl.

AtmosphereN2 protection/Schlenk line for Sonogashira and C1 preparation; not specified for bromination and hydrolysis.

TemperatureRoom temperature, 90 C, 100 C, reflux depending on step.

Time4 h, 10 h, 12 h, overnight, 24 h depending on step.

Oxidant / reductantBr2 bromination; NaSO3 quench/reductant; KOH hydrolysis followed by HCl acidification.

Work-upSolvent removal in vacuo, extraction, water washes, MgSO4 drying, silica chromatography, suction filtration and extensive water washing.

Scalability contextMulti-step organic linker synthesis on tens to hundreds of milligrams; no scale-up discussion.

Show 14 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	4-Bromothioanisole	0.9 g, 4.5 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Additive	Pd(PPh3)2Cl2	63 mg, 0.09 mmol; later 18 mg, 0.024 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Additive	PPh3	39 mg, 0.45 mmol; later 36 mg	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Additive	CuI	22.5 mg, 0.135 mmol; later 7.5 mg	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Other	Trimethylsilylacetylene	0.525 g, 5.4 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Base	Triethylamine	10 mL; later 2.5 mL	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Base	K2CO3	0.1 eq.; 1.38 g, 10 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Other	Methyl 4-hydroxybenzoate	0.67 g, 4.4 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Other	Pentaerythritol tetrabromide	388 mg, 1 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Oxidant	Br2	1.04 g, 6.40 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Reductant	NaSO3	200 mg	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Other	C2	200 mg, 0.20 mmol	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Base	KOH	3 M methanol/water (1:1 v:v) solution, 12 mL	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1
Acid	HCl	10% aqueous	SI p.S3-S6 · Scheme S1 and linker synthesis · Scheme S1