Synthesis · Tunable Capacitive Behavior in Metallopolymer-based Electrochromic Thin Film Supercapacitors

9 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Drop Cast

p009 · Determination of Resistivity and Electrical Conductivity via 4-Probe Measurements

Linker precursorspoly-Fe-L1, poly-Fe-L2 or poly-Fe-L3 metallopolymer

Solventsmethanol/dichloromethane (1:1 v/v, 200 microL)

Atmospherenot specified

Substrate orientationglass substrate

Work-upDrop-cast on glass; thickness measured by Bruker Dektak XT profilometer

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	metallopolymer	2 mg	p009 · Determination of Resistivity and Electrical Conductivity via 4-Probe Measurements
Solvent	methanol/dichloromethane	200 microL · 1:1 v/v	p009 · Determination of Resistivity and Electrical Conductivity via 4-Probe Measurements

Complete recipeSource: SI

Route 2: Other

p004 · Synthesis of L1 · Scheme S2

Metal precursorsPd(PPh3)2Cl2 catalyst

Linker precursorstetrabromobenzene 4; terpyridine phenylboronic acid 3

SolventsH2O (10 mL), toluene (30 mL), tert-butyl alcohol (1.5 mL); chromatography CHCl3/MeOH (9:1)

AdditivesNa2CO3 (806 mg, 30 eq)

Atmosphere3 argon/evacuation cycles; added solvents under argon; sealed pressure tube

Temperature110

Time144

Work-upCool to room temperature; extract with chloroform; wash with brine; dry over Na2SO4; concentrate in vacuo; silica column chromatography

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Tetrabromobenzene 4	100 mg, 0.25 mmol	p004 · Synthesis of L1 · Scheme S2
Linker	boronic acid 3	538 mg, 6 eq	p004 · Synthesis of L1 · Scheme S2
Additive	Pd(PPh3)2Cl2	53.7 mg, 0.3 eq	p004 · Synthesis of L1 · Scheme S2
Base	Na2CO3	806 mg, 30 eq	p004 · Synthesis of L1 · Scheme S2
Solvent	H2O	10 mL	p004 · Synthesis of L1 · Scheme S2
Solvent	toluene	30 mL	p004 · Synthesis of L1 · Scheme S2
Solvent	tert-butyl alcohol	1.5 mL	p004 · Synthesis of L1 · Scheme S2

Complete recipeSource: SI

Route 3: Other

p006 · Step 3: Synthesis of L2 · Scheme S3

Metal precursorsPd(PPh3)2Cl2 catalyst

Linker precursors1,1,2,2-tetrakis(4-bromophenyl)ethene 7; terpyridine phenylboronic acid 3

SolventsH2O (10 mL), toluene (30 mL), tert-butyl alcohol (1.5 mL); chromatography CHCl3/MeOH (9:1)

AdditivesNa2CO3 (490.6 mg, 4.62 mmol)

Atmosphere3 argon/evacuation cycles; solvents added under argon; sealed pressure tube

Temperature110

Time144

Work-upCool to room temperature; extract with CHCl3; wash with brine; dry over Na2SO4; concentrate in vacuo; silica column chromatography

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,1,2,2-tetrakis(4-bromophenyl)ethene 7	100 mg, 0.15 mmol	p006 · Step 3: Synthesis of L2 · Scheme S3
Linker	boronic acid 3	327 mg, 0.92 mmol	p006 · Step 3: Synthesis of L2 · Scheme S3
Additive	Pd(PPh3)2Cl2	32 mg, 0.046 mmol	p006 · Step 3: Synthesis of L2 · Scheme S3
Base	Na2CO3	490.6 mg, 4.62 mmol	p006 · Step 3: Synthesis of L2 · Scheme S3
Solvent	H2O	10 mL	p006 · Step 3: Synthesis of L2 · Scheme S3
Solvent	toluene	30 mL	p006 · Step 3: Synthesis of L2 · Scheme S3
Solvent	tert-butyl alcohol	1.5 mL	p006 · Step 3: Synthesis of L2 · Scheme S3

Complete recipeSource: SI

Route 4: Other

p006-p007 · Synthesis of L3 · Scheme S4

Metal precursorsPd(PPh3)2Cl2 catalyst

Linker precursors3,3',5,5'-tetrabromo-2,2'-bithiophene 8; terpyridine phenylboronic acid 3

SolventsH2O (10 mL), toluene (30 mL), tert-butyl alcohol (1.5 mL); chromatography CHCl3/MeOH (9:1)

AdditivesNa2CO3 (658 mg, 6.21 mmol)

Atmosphere3 argon/evacuation cycles; solvents added under argon; sealed pressure tube

Temperature110

Time144

Work-upCool to room temperature; extract with chloroform; wash with brine; dry over Na2SO4; concentrate in vacuo; silica column chromatography

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	3,3',5,5'-Tetrabromo-2,2'-bithiophene 8	100 mg, 0.207 mmol	p006-p007 · Synthesis of L3 · Scheme S4
Linker	boronic acid 3	438 mg, 1.24 mmol	p006-p007 · Synthesis of L3 · Scheme S4
Additive	Pd(PPh3)2Cl2	43 mg, 0.062 mmol	p006-p007 · Synthesis of L3 · Scheme S4
Base	Na2CO3	658 mg, 6.21 mmol	p006-p007 · Synthesis of L3 · Scheme S4
Solvent	H2O	10 mL	p006-p007 · Synthesis of L3 · Scheme S4
Solvent	toluene	30 mL	p006-p007 · Synthesis of L3 · Scheme S4
Solvent	tert-butyl alcohol	1.5 mL	p006-p007 · Synthesis of L3 · Scheme S4

Complete recipeSource: Both

Route 5: Other

p007 · Synthesis of the Metallopolymers

Metal precursorsFeCl2.4H2O (24.9 mg, 2 equiv.)

Linker precursorsL1 (32.5 mg)

SolventsMeOH (10.0 mL) for metal solution; CHCl3 (10.0 mL) for ligand solution

AdditivesWater (15 mL) saturated with potassium hexafluorophosphate

Atmospheredark, room temperature; atmosphere not otherwise specified

Temperatureroom temperature

Time2 h metal/ligand stirring plus 0.5 h after PF6 addition

Work-upRemove solvent under reduced pressure to 25% of initial volume; add PF6-saturated water; filter precipitate; wash with DI water (10 mL x 3)

Activationdried in vacuum oven

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl2.4H2O	24.9 mg, 2 equiv.	p007 · Synthesis of the Metallopolymers
Linker	L1	32.5 mg	p007 · Synthesis of the Metallopolymers
Solvent	MeOH	10.0 mL	p007 · Synthesis of the Metallopolymers
Solvent	CHCl3	10.0 mL	p007 · Synthesis of the Metallopolymers
Additive	potassium hexafluorophosphate-saturated water	15 mL	p007 · Synthesis of the Metallopolymers

Complete recipeSource: Both

Route 6: Other

p007 · Synthesis of the Metallopolymers

Metal precursorsFeCl2.4H2O (24.9 mg, 2 equiv.)

Linker precursorsL2 (39.0 mg)

SolventsMeOH (10.0 mL) for metal solution; CHCl3 (10.0 mL) for ligand solution

AdditivesWater (15 mL) saturated with potassium hexafluorophosphate

Atmospheredark, room temperature; atmosphere not otherwise specified

Temperatureroom temperature

Time2 h metal/ligand stirring plus 0.5 h after PF6 addition

Work-upRemove solvent under reduced pressure to 25% of initial volume; add PF6-saturated water; filter precipitate; wash with DI water (10 mL x 3)

Activationdried in vacuum oven

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl2.4H2O	24.9 mg, 2 equiv.	p007 · Synthesis of the Metallopolymers
Linker	L2	39.0 mg	p007 · Synthesis of the Metallopolymers
Solvent	MeOH	10.0 mL	p007 · Synthesis of the Metallopolymers
Solvent	CHCl3	10.0 mL	p007 · Synthesis of the Metallopolymers
Additive	potassium hexafluorophosphate-saturated water	15 mL	p007 · Synthesis of the Metallopolymers

Complete recipeSource: Both

Route 7: Other

p003 · Syntheses of the Metallopolymers

Metal precursorsFeCl2.4H2O (24.9 mg, 2 equiv.)

Linker precursorsL3 (34.9 mg)

SolventsMeOH (10.0 mL) for metal solution; CHCl3 (10.0 mL) for ligand solution

AdditivesWater (15 mL) saturated with potassium hexafluorophosphate

Atmospheredark, room temperature; atmosphere not otherwise specified

Temperatureroom temperature

Time2 h metal/ligand stirring plus 0.5 h after PF6 addition

Work-upRemove solvent under reduced pressure to 25% of initial volume; add PF6-saturated water; filter precipitate; wash with DI water (10 mL x 3)

Activationdried in vacuum oven

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl2.4H2O	24.9 mg, 2 equiv.	p003 · Syntheses of the Metallopolymers
Linker	L3	34.9 mg	p003 · Syntheses of the Metallopolymers
Solvent	MeOH	10.0 mL	p003 · Syntheses of the Metallopolymers
Solvent	CHCl3	10.0 mL	p003 · Syntheses of the Metallopolymers
Additive	potassium hexafluorophosphate-saturated water	15 mL	p003 · Syntheses of the Metallopolymers

Partial recipeSource: Both

Route 8: Other

p009 · Preparation of the Electrodes and Electrochemical Measurements

Linker precursorspoly-Fe-L1, poly-Fe-L2 or poly-Fe-L3 metallopolymer

Additivesactivated charcoal; polytetrafluoroethylene

Atmosphereroom temperature electrochemical testing

Temperatureroom temperature

Substrate orientation1 cm2 electrode area; symmetric two-electrode configuration

Work-upMix corresponding metallopolymer (1.0 mg) with activated charcoal and PTFE in 8:1:1 mass ratio

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	corresponding metallopolymer	1.0 mg	p009 · Preparation of the Electrodes and Electrochemical Measurements
Additive	activated charcoal	8:1:1 metallopolymer:charcoal:PTFE mass-ratio component	p009 · Preparation of the Electrodes and Electrochemical Measurements
Additive	polytetrafluoroethylene	8:1:1 metallopolymer:charcoal:PTFE mass-ratio component	p009 · Preparation of the Electrodes and Electrochemical Measurements

Partial recipeSource: Both

Route 9: Drop Cast

p005 · Electrochemistry and Spectroelectrochemistry · Figure 5

Linker precursorspoly-Fe-L1, poly-Fe-L2 or poly-Fe-L3 metallopolymer

SolventsMeOH for TCO drop-casting; dry acetonitrile electrolyte during measurements

Atmosphereroom temperature

Temperatureroom temperature

Substrate orientationTCO/FTO substrates for electrochemistry/spectroelectrochemistry; freshly cleaved mica for AFM

Work-upDrop-cast to form thin films; no spray-coating required in this work

Scalability contextSimple drop-casting gave thicker, slightly less uniform films than earlier multilayer spray coating.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	metallopolymer	Not specified	p005 · Electrochemistry and Spectroelectrochemistry · Figure 5
Solvent	MeOH	Not specified	p005 · Electrochemistry and Spectroelectrochemistry · Figure 5