Synthesis · Selenium-Substitution Strategy for Enhanced Mobility, Tunable Bandgap, and Improved Electrochemical Energy Storage in Semiconducting Conjugated Coordination Polymers

7 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

2 · Synthesis of Ag4TSHQ

Metal precursorssilver perchlorate

Linker precursorsTSHQ

Solventsdegassed water

Atmosphereargon

Temperature80

Time24

Work-upCool to room temperature, filter black product, wash with water, methanol and ether.

ActivationDried under vacuum at 60 deg C for 24 h.

Scalability context163 mg product, 95% yield from 0.2 mmol TSHQ.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TSHQ	0.2 mmol, 85.2 mg	2 · Synthesis of Ag4TSHQ
Metal Source	silver perchlorate	0.8 mmol, 165.9 mg	2 · Synthesis of Ag4TSHQ
Solvent	degassed water	50 mL	2 · Synthesis of Ag4TSHQ
Solvent	water	wash	2 · Synthesis of Ag4TSHQ
Solvent	methanol	wash	2 · Synthesis of Ag4TSHQ
Solvent	ether	wash	2 · Synthesis of Ag4TSHQ

Complete recipeSource: SI

Route 2: Other

2 · Synthesis of mixed-ligand Ag4TXHQ

Metal precursorssilver acetate

Linker precursorsTTHQ and TSHQ, total ligand 0.2 mmol, TTHQ:TSHQ = 11:1

Solventsdegassed methanol

Atmosphereargon

Temperature80

Time24

Work-upPost-processing steps same as Ag4TSHQ: cool, filter, wash with water/methanol/ether.

ActivationDried under vacuum at 60 deg C for 24 h by same post-processing as Ag4TSHQ.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TTHQ	part of 0.2 mmol total ligand, ratio 11:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Linker	TSHQ	part of 0.2 mmol total ligand, ratio 11:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Metal Source	silver acetate	0.8 mmol	2 · Synthesis of mixed-ligand Ag4TXHQ
Solvent	degassed methanol	50 mL	2 · Synthesis of mixed-ligand Ag4TXHQ

Complete recipeSource: SI

Route 3: Other

2 · Synthesis of mixed-ligand Ag4TXHQ

Metal precursorssilver acetate

Linker precursorsTTHQ and TSHQ, total ligand 0.2 mmol, TTHQ:TSHQ = 1:1

Solventsdegassed methanol

Atmosphereargon

Temperature80

Time24

Work-upPost-processing steps same as Ag4TSHQ: cool, filter, wash with water/methanol/ether.

ActivationDried under vacuum at 60 deg C for 24 h by same post-processing as Ag4TSHQ.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TTHQ	part of 0.2 mmol total ligand, ratio 1:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Linker	TSHQ	part of 0.2 mmol total ligand, ratio 1:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Metal Source	silver acetate	0.8 mmol	2 · Synthesis of mixed-ligand Ag4TXHQ
Solvent	degassed methanol	50 mL	2 · Synthesis of mixed-ligand Ag4TXHQ

Complete recipeSource: SI

Route 4: Other

2 · Synthesis of mixed-ligand Ag4TXHQ

Metal precursorssilver acetate

Linker precursorsTTHQ and TSHQ, total ligand 0.2 mmol, TTHQ:TSHQ = 3:1

Solventsdegassed methanol

Atmosphereargon

Temperature80

Time24

Work-upPost-processing steps same as Ag4TSHQ: cool, filter, wash with water/methanol/ether.

ActivationDried under vacuum at 60 deg C for 24 h by same post-processing as Ag4TSHQ.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TTHQ	part of 0.2 mmol total ligand, ratio 3:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Linker	TSHQ	part of 0.2 mmol total ligand, ratio 3:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Metal Source	silver acetate	0.8 mmol	2 · Synthesis of mixed-ligand Ag4TXHQ
Solvent	degassed methanol	50 mL	2 · Synthesis of mixed-ligand Ag4TXHQ

Complete recipeSource: SI

Route 5: Other

2 · Synthesis of mixed-ligand Ag4TXHQ

Metal precursorssilver acetate

Linker precursorsTTHQ and TSHQ, total ligand 0.2 mmol, TTHQ:TSHQ = 7:1

Solventsdegassed methanol

Atmosphereargon

Temperature80

Time24

Work-upPost-processing steps same as Ag4TSHQ: cool, filter, wash with water/methanol/ether.

ActivationDried under vacuum at 60 deg C for 24 h by same post-processing as Ag4TSHQ.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TTHQ	part of 0.2 mmol total ligand, ratio 7:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Linker	TSHQ	part of 0.2 mmol total ligand, ratio 7:1	2 · Synthesis of mixed-ligand Ag4TXHQ
Metal Source	silver acetate	0.8 mmol	2 · Synthesis of mixed-ligand Ag4TXHQ
Solvent	degassed methanol	50 mL	2 · Synthesis of mixed-ligand Ag4TXHQ

Complete recipeSource: SI

Route 6: Other

1 · Synthesis of 2,3,5,6-tetrakis(tert-butylselanyl)-1,4-hydroquinone

Linker precursorsp-chloranil

Solventsanhydrous tetrahydrofuran; dichloromethane extraction; methanol recrystallisation

Additivesanhydrous magnesium sulfate drying agent

Atmosphereargon

Temperature-78 then room temperature

Time1 h after warming, then 24 h after p-chloranil addition

Oxidant / reductantselenium powder; tert-butyl lithium

Work-upWater quench, extracted three times with dichloromethane, organic layer dried over anhydrous magnesium sulfate, solvent removed by rotary evaporation, recrystallised from methanol.

Scalability contextYield approximately 975 mg (15%).

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Selenium powder	60 mmol, 4.74 g	1 · Synthesis of 2,3,5,6-tetrakis(tert-butylselanyl)-1,4-hydroquinone
Solvent	anhydrous tetrahydrofuran	50 mL	1 · Synthesis of 2,3,5,6-tetrakis(tert-butylselanyl)-1,4-hydroquinone
Reductant	tert-butyl lithium	60 mmol, 46 mL · 1.3 M in n-heptane	1 · Synthesis of 2,3,5,6-tetrakis(tert-butylselanyl)-1,4-hydroquinone
Linker	p-chloranil	10 mmol, 2.45 g	1 · Synthesis of 2,3,5,6-tetrakis(tert-butylselanyl)-1,4-hydroquinone
Solvent	dichloromethane	three extractions	1 · Synthesis of 2,3,5,6-tetrakis(tert-butylselanyl)-1,4-hydroquinone
Solvent	methanol	recrystallisation solvent	1 · Synthesis of 2,3,5,6-tetrakis(tert-butylselanyl)-1,4-hydroquinone

Complete recipeSource: SI

Route 7: Other

1-2 · Synthesis of 2,3,5,6-tetraselenol-1,4-hydroquinone (TSHQ)

Linker precursors(tBu)4TSHQ

Solventsfluorobenzene; degassed water

AdditivesBBr3

Atmosphereargon for transfer/water step

Temperature75

Time12 h heating; then stirred in degassed water

Work-upCool to precipitate TSHQ(BBr), transfer under argon, add degassed water, stir, collect orange precipitate by filtration and dry under vacuum.

Activationvacuum drying

Scalability context319 mg, 75% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	(tBu)4TSHQ	1 mmol, 650 mg	1-2 · Synthesis of 2,3,5,6-tetraselenol-1,4-hydroquinone (TSHQ)
Solvent	fluorobenzene	20 mL	1-2 · Synthesis of 2,3,5,6-tetraselenol-1,4-hydroquinone (TSHQ)
Additive	BBr3	6 mmol, 0.6 mL	1-2 · Synthesis of 2,3,5,6-tetraselenol-1,4-hydroquinone (TSHQ)
Solvent	degassed water	not specified	1-2 · Synthesis of 2,3,5,6-tetraselenol-1,4-hydroquinone (TSHQ)