Synthesis · A conducting coordination polymer based on assembled Cu9 cages

2 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.S-2 · Synthesis and Characterization

Metal precursorsCu(BF4)2.xH2O (0.115 g, 0.48 mmol)

Linker precursors2-dpds (2,2'-dipyridyldisulfide; 0.106 g, 0.48 mmol)

Solvents12 mL MeOH:CH2Cl2 (1:1)

Atmospheresealed 70 mL TFM vessel; no inert atmosphere stated

Temperature140

Time2 h hold after 20 min ramp; cooled to room temperature in 4 h

Oxidant / reductantNo separate reductant added; Cu(II) to Cu(I) reduction discussed as possibly emphasised under microwave conditions, with methanol, N-containing ligands and thiolate groups as possible contributors.

Work-upYellow crystals of 1 were obtained, washed with CH2Cl2 and dried in air; yield 0.500 g, 55% based on Cu.

Activationnone reported

Scalability contextPerformed in a 70 mL microwave vessel with a 12 mL solvent charge; no scale-up study reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(BF4)2.xH2O	0.115 g, 0.48 mmol	SI p.S-2 · Synthesis and Characterization
Linker	2-dpds (2,2'-dipyridyldisulfide)	0.106 g, 0.48 mmol	SI p.S-2 · Synthesis and Characterization
Solvent	MeOH:CH2Cl2 (1:1)	12 mL	SI p.S-2 · Synthesis and Characterization

Complete recipeSource: Both

Route 2: Solvothermal

SI p.S-2 · Synthesis and Characterization

Metal precursorsCu(BF4)2.xH2O (0.115 g, 0.48 mmol) from shared reaction

Linker precursors2-dpds (0.106 g, 0.48 mmol) from shared reaction; converted partly to 2-dps

Solvents12 mL MeOH:CH2Cl2 (1:1), followed by mother liquor/filtrate crystallisation

Atmospheresealed microwave vessel for initial reaction; refrigerator storage not further specified

Temperature140 for initial reaction; 0 for filtrate crystallisation

Time2 h initial microwave hold; 3 weeks filtrate standing at 0 C

Oxidant / reductantReaction involves Cu(II) chemistry and S-S/C-S cleavage of 2-dpds; no separate redox reagent added.

Work-upAfter removal of compound 1 crystals, filtrate was allowed to stand in a refrigerator at 0 C for 3 weeks; compound 2 crystals formed with elemental sulfur crystals; yield 0.028 g, 4% based on Cu.

Activationnone reported

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(BF4)2.xH2O	0.115 g, 0.48 mmol in shared reaction	SI p.S-2 · Synthesis and Characterization
Linker	2-dpds (2,2'-dipyridyldisulfide)	0.106 g, 0.48 mmol in shared reaction	SI p.S-2 · Synthesis and Characterization
Solvent	MeOH:CH2Cl2 (1:1)	12 mL in shared reaction	SI p.S-2 · Synthesis and Characterization