Synthesis · Conjugated Metal-Organic Macrocycles: Synthesis, Characterization, and Electrical Conductivity

5 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Vague recipeSource: SI

Route 1: Unknown

SI S18 · Supplementary tables · Table S7

Metal precursorsnot specified in this paper; Cu3(HHTP)2 synthesised according to previously reported procedures

Linker precursorsHHTP, per Figure 1 parent framework schematic

Solventsnot specified for control pellet recipe in this paper

Work-upnot reported

Activationnot reported

Complete recipeSource: Both

Route 2: Other

SI S4 · Macrocycle synthesis

Metal precursorsCu(OAc)2.H2O (0.026 g, 0.132 mmol, 1.10 equiv)

Linker precursorsH4TOTP-OC18 (0.100 g, 0.121 mmol, 1.00 equiv)

SolventsTHF (10.5 mL) for ligand; DMF (4.5 mL) for metal

Atmosphereair during addition per main/Fig. 1; Teflon-taped vials; N2 purge during drying

Temperature60

Time24

Oxidant / reductantCu(OAc)2.H2O and air; main text proposes aerobic oxidation to TOTP-OR2- with bridging dioxolene units in [sq,sq]2- state.

Work-upfiltered; washed with 1:1 THF:DMF (3x10 mL); filtered and rinsed with additional DMF

Activationdried under purging N2 at 35 C for 3 h

Scalability contextIsolated 88% yield (93.8 mg, 0.016 mmol).

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4TOTP-OC18 (0.100 g, 0.121 mmol, 1.00 equiv)	0.100 g, 0.121 mmol, 1.00 equiv	SI S4 · Macrocycle synthesis
Metal Source	Cu(OAc)2.H2O (0.026 g, 0.132 mmol, 1.10 equiv)	1.10 equiv	SI S4 · Macrocycle synthesis
Solvent	THF (10.5 mL) for ligand; DMF (4.5 mL) for metal	Not specified	SI S4 · Macrocycle synthesis
Oxidant	air	ambient	SI S4 · Macrocycle synthesis

Complete recipeSource: Both

Route 3: Other

SI S4 · Macrocycle synthesis

Metal precursorscopper acetate monohydrate (Cu(OAc)2.H2O) (0.116 g, 0.289 mmol, 1.10 equiv)

Linker precursorsH4TOTP-OC2 (0.100 g, 0.263 mmol, 1.00 equiv)

SolventsDMF (10 mL for ligand; 20 mL for metal)

Atmosphereair/capped vial; both solutions sonicated 5 min

Temperatureroom temperature

Time336

Oxidant / reductantCu(OAc)2.H2O and air; main text proposes aerobic oxidation to TOTP-OR2- with bridging dioxolene units in [sq,sq]2- state.

Work-upcentrifuged; washed with DMF (3x15 mL) and EtOAc (11x15 mL) at room temperature

Activationnone reported

Scalability contextIsolated 67% yield (77.6 mg, 0.029 mmol).

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4TOTP-OC2 (0.100 g, 0.263 mmol, 1.00 equiv)	0.100 g, 0.263 mmol, 1.00 equiv	SI S4 · Macrocycle synthesis
Metal Source	copper acetate monohydrate (Cu(OAc)2.H2O) (0.116 g, 0.289 mmol, 1.10 equiv)	1.10 equiv	SI S4 · Macrocycle synthesis
Solvent	DMF (10 mL for ligand; 20 mL for metal)	Not specified	SI S4 · Macrocycle synthesis
Oxidant	air	ambient	SI S4 · Macrocycle synthesis

Complete recipeSource: Both

Route 4: Other

SI S4 · Macrocycle synthesis

Metal precursorsCu(OAc)2.H2O (0.151 g, 0.252 mmol, 1.10 equiv)

Linker precursorsH4TOTP-OC4 (0.100 g, 0.229 mmol, 1.00 equiv)

SolventsDMF (10 mL for ligand; 20 mL for metal)

Atmosphereair/capped vial; both solutions sonicated 5 min

Temperatureroom temperature

Time144-336

Oxidant / reductantCu(OAc)2.H2O and air; main text proposes aerobic oxidation to TOTP-OR2- with bridging dioxolene units in [sq,sq]2- state.

Work-upcentrifuged; washed with DMF (3x15 mL) and EtOAc (11x15 mL) at room temperature

Activationnone reported

Scalability contextIsolated 83% yield (94.2 mg, 0.031 mmol).

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4TOTP-OC4 (0.100 g, 0.229 mmol, 1.00 equiv)	0.100 g, 0.229 mmol, 1.00 equiv	SI S4 · Macrocycle synthesis
Metal Source	Cu(OAc)2.H2O (0.151 g, 0.252 mmol, 1.10 equiv)	1.10 equiv	SI S4 · Macrocycle synthesis
Solvent	DMF (10 mL for ligand; 20 mL for metal)	Not specified	SI S4 · Macrocycle synthesis
Oxidant	air	ambient	SI S4 · Macrocycle synthesis

Complete recipeSource: Both

Route 5: Other

SI S4 · Macrocycle synthesis

Metal precursorsCu(OAc)2.H2O (0.223 g, 0.252 mmol, 1.10 equiv)

Linker precursorsH4TOTP-OC6 (0.100 g, 0.203 mmol, 1.00 equiv)

SolventsDMF (10 mL for ligand; 20 mL for metal)

Atmosphereair/capped vial; both solutions sonicated 5 min

Temperatureroom temperature

Time144-336

Oxidant / reductantCu(OAc)2.H2O and air; main text proposes aerobic oxidation to TOTP-OR2- with bridging dioxolene units in [sq,sq]2- state.

Work-upcentrifuged; washed with DMF (3x15 mL) and EtOAc (11x15 mL) at room temperature

Activationnone reported

Scalability contextIsolated 85% yield (95.1 mg, 0.029 mmol).

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4TOTP-OC6 (0.100 g, 0.203 mmol, 1.00 equiv)	0.100 g, 0.203 mmol, 1.00 equiv	SI S4 · Macrocycle synthesis
Metal Source	Cu(OAc)2.H2O (0.223 g, 0.252 mmol, 1.10 equiv)	1.10 equiv	SI S4 · Macrocycle synthesis
Solvent	DMF (10 mL for ligand; 20 mL for metal)	Not specified	SI S4 · Macrocycle synthesis
Oxidant	air	ambient	SI S4 · Macrocycle synthesis