Synthesis · Linker-Based Bandgap Tuning in Conductive MOF Solid Solutions

6 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Hydrothermal

S5 · Base addition sequence effect · Figure S2

Metal precursorsCu(NO3)2.2.5H2O (0.017 g, 0.072 mmol)

Linker precursorsTATHB (0.010 g, 0.036 mmol)

SolventsH2O, 10 mL copper solution plus 5 mL ligand solution

Additives60 uL of 6 M NH4OH added before ligand in base-first variant; compared with base-later route

Atmosphereair

Temperatureroom temperature; dried at 60 deg C

Time1 h reaction; 1 h vacuum drying

Work-upWashed and centrifuged with H2O and acetone (2 x 5 mL each).

Scalability contextOptimisation series only.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	0.017 g, 0.072 mmol	S5 · Base addition sequence effect · Figure S2
Linker	TATHB	0.010 g, 0.036 mmol	S5 · Base addition sequence effect · Figure S2
Solvent	H2O	10 mL + 5 mL	S5 · Base addition sequence effect · Figure S2
Base	NH4OH	60 uL · 6 M	S5 · Base addition sequence effect · Figure S2

Complete recipeSource: SI

Route 2: Hydrothermal

S4 · Concentration effect · Figure S1

Metal precursorsCu(NO3)2.2.5H2O (0.017 g, 0.072 mmol)

Linker precursorsTATHB (0.010 g, 0.036 mmol)

SolventsH2O, copper solution varied between 10 mL and 5 mL; ligand solution 5 mL

Additives60 uL of 6 M NH4OH

Atmosphereair

Temperatureroom temperature; dried at 60 deg C

Time1 h reaction; 1 h vacuum drying

Work-upWashed and centrifuged with H2O and acetone (2 x 5 mL each).

Scalability contextOptimisation series only.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	0.017 g, 0.072 mmol	S4 · Concentration effect · Figure S1
Linker	TATHB	0.010 g, 0.036 mmol	S4 · Concentration effect · Figure S1
Solvent	H2O	10 or 5 mL copper solution; 5 mL ligand solution	S4 · Concentration effect · Figure S1
Base	NH4OH	60 uL · 6 M	S4 · Concentration effect · Figure S1

Complete recipeSource: Both

Route 3: Hydrothermal

S2 · Synthesis of Cu-TATHB

Metal precursorsCu(NO3)2.2.5H2O (0.017 g, 0.072 mmol)

Linker precursorsTATHB.3HCl (0.010 g, 0.036 mmol)

SolventsH2O, 10 mL for copper solution plus 5 mL for ligand solution

Additives60 uL of 6 M NH4OH

Atmosphereair

Temperatureroom temperature; dried at 60 deg C

Time1 h reaction; 1 h vacuum drying

Work-upWashed and centrifuged with H2O and acetone (2 x 5 mL each).

ActivationFor BET analysis, evacuated to 50 umHg at 5 mmHg s^-1, heated to 80 deg C at 10 deg C min^-1, held 2 h.

Scalability contextSmall-batch powder synthesis; no scale-up data reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	0.017 g, 0.072 mmol	S2 · Synthesis of Cu-TATHB
Linker	TATHB.3HCl	0.010 g, 0.036 mmol	S2 · Synthesis of Cu-TATHB
Solvent	H2O	10 mL + 5 mL	S2 · Synthesis of Cu-TATHB
Base	NH4OH	60 uL · 6 M	S2 · Synthesis of Cu-TATHB

Complete recipeSource: SI

Route 4: Hydrothermal

S6 · Reaction time effect · Figure S3

Metal precursorsCu(NO3)2.2.5H2O (0.017 g, 0.072 mmol)

Linker precursorsTATHB (0.010 g, 0.036 mmol)

SolventsH2O, 10 mL copper solution plus 5 mL ligand solution

Additives60 uL of 6 M NH4OH

Atmosphereair

Temperatureroom temperature; dried at 60 deg C

Time1, 2, 4, or 8 h reaction; 1 h vacuum drying

Work-upWashed and centrifuged with H2O and acetone (2 x 5 mL each).

Scalability contextOptimisation series only.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	0.017 g, 0.072 mmol	S6 · Reaction time effect · Figure S3
Linker	TATHB	0.010 g, 0.036 mmol	S6 · Reaction time effect · Figure S3
Solvent	H2O	10 mL + 5 mL	S6 · Reaction time effect · Figure S3
Base	NH4OH	60 uL · 6 M	S6 · Reaction time effect · Figure S3

Complete recipeSource: SI

Route 5: Hydrothermal

S2 · Synthesis of Cu3(HAB)x(TATHB)2-x

Metal precursorsCu(NO3)2.2.5H2O (0.017 g, 0.072 mmol)

Linker precursors5 mL HAB/TATHB mixed aqueous stock solution with HAB:TATHB mole ratios 1:0, 3:1, 1:1, and 1:3; x = 0 end-member prepared as Cu-TATHB/TATHB-only recipe.

SolventsH2O, 5 mL copper solution plus 5 mL mixed linker solution

Additives60 uL of 6 M NH4OH

Atmosphereair, as implied by the Cu-TATHB route; not restated for solid-solution route

Temperatureroom temperature; dried at 60 deg C

Time1 h reaction; 1 h vacuum drying

Work-upWashed and centrifuged with H2O and acetone (2 x 5 mL each).

ActivationNo separate activation reported for solid-solution characterisation beyond vacuum drying; BET activation specified only for Cu-TATHB.

Scalability contextSmall-batch powder synthesis; no scale-up data reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	0.017 g, 0.072 mmol	S2 · Synthesis of Cu3(HAB)x(TATHB)2-x
Linker	HAB/TATHB mixed linker aqueous stock solution	5 mL · mole ratios 1:0, 3:1, 1:1, 1:3	S2 · Synthesis of Cu3(HAB)x(TATHB)2-x
Solvent	H2O	5 mL + 5 mL	S2 · Synthesis of Cu3(HAB)x(TATHB)2-x
Base	NH4OH	60 uL · 6 M	S2 · Synthesis of Cu3(HAB)x(TATHB)2-x

Partial recipeSource: SI

Route 6: Other

S13 · Control experiment · Figure S9

Metal precursorsCopper precursor not re-specified; based on optimised Cu3(TATHB)2 condition

Linker precursorsHAB/THQ or TATHB/THQ with 1:1 ligand stoichiometry

SolventsNot fully restated; based on optimised aqueous condition

AdditivesCondition 3 used ethylenediamine as a base; other base details not fully specified

Atmosphereambient condition, inert condition, and inert condition with ethylenediamine

Temperaturenot fully restated

Timenot fully restated

Work-upnot fully restated

Scalability contextNegative control; no scale-up data.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HAB/THQ	1:1 stoichiometry	S13 · Control experiment · Figure S9
Linker	TATHB/THQ	1:1 stoichiometry	S13 · Control experiment · Figure S9
Base	ethylenediamine	condition 3 only	S13 · Control experiment · Figure S9