Synthesis · Near IR Bandgap Semiconducting 2D Conjugated Metal-Organic Framework with Rhombic Lattice and High Mobility

4 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Solvothermal

3 · Results and Discussion · Figure 1a

Metal precursorsCu(II), copper source optimised

Linker precursorsOHPTP ligand

Solventsneutral water-DMF mixture, 7:3

Temperature85

Time24

Work-upblack powder product; detailed workup in SI

Activationdetailed activation in SI

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	OHPTP ligand	Not specified	3 · Results and Discussion · Figure 1a
Metal Source	Cu(II) source	Not specified	3 · Results and Discussion · Figure 1a
Solvent	water-DMF	7:3	3 · Results and Discussion · Figure 1a

Complete recipeSource: SI

Route 2: Solvothermal

6 · Optimized Synthesis of Cu2(OHPTP) · Scheme S2

Metal precursorsCu(OAc)2.H2O

Linker precursorsOHPTP 5

Solvents2.3 mL deionised water; 1.0 mL DMF; dry acetone for activation

Atmospherenot specified for MOF formation; activation under vacuum

Temperature85; activation at 100 under vacuum

Timeovernight for synthesis; acetone exchange daily for 7 d; vacuum overnight; 100 deg C vacuum overnight

Work-upcool to room temperature; filter black precipitate; wash with 150 mL water and 20 mL acetone

Activationsolvent exchanged with 10 mL dry acetone each day for 7 d, filtered, vacuum overnight, then heated under vacuum to 100 deg C overnight

Scalability contextOptimised recipe uses 12 mg linker in a 10 mL glass vial.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	OHPTP 5	12 mg, 23.7 umol, 1 eq.	6 · Optimized Synthesis of Cu2(OHPTP) · Scheme S2
Metal Source	Cu(OAc)2.H2O	9.6 mg, 48.1 umol, 2 eq.	6 · Optimized Synthesis of Cu2(OHPTP) · Scheme S2
Solvent	deionized water	2.3 mL	6 · Optimized Synthesis of Cu2(OHPTP) · Scheme S2
Solvent	DMF	1.0 mL	6 · Optimized Synthesis of Cu2(OHPTP) · Scheme S2
Solvent	dry acetone	10 mL each day for 7 d	6 · Optimized Synthesis of Cu2(OHPTP) · Scheme S2

Complete recipeSource: SI

Route 3: Other

5 · Section B: Synthesis of OHPTP · Scheme S1

Metal precursorsPd(PPh3)4 catalyst for Suzuki step; FeCl3 for Scholl oxidation; BBr3 for demethylation

Linker precursors1,2,4,5-tetrabromobenzene; 3,4-dimethoxyphenylboronic acid

SolventsDME, aqueous K2CO3, DCM, nitromethane, MeOH, ethanol

AdditivesK2CO3 base; Al2O3 plug for purification

Atmosphereargon protection/argon stream for each synthetic step

TemperatureSuzuki reflux overnight; Scholl 0 deg C to room temperature overnight; demethylation -78 deg C to room temperature overnight

Timeovernight for each of three steps, plus specified sonication/quench/workup periods

Oxidant / reductantFeCl3 promoted Scholl reaction; BBr3 deprotection

Work-upprecipitation in water or MeOH, filtration, vacuum drying, Al2O3 plug, recrystallisation, centrifugation, degassed solvent washing

Scalability contextMulti-step ligand synthesis reported from gram-scale intermediates to 0.71 g OHPTP.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,2,4,5-Tetrabrombenzene	2.00 g, 5.08 mmol, 1.0 eq.	5 · Section B: Synthesis of OHPTP · Scheme S1
Linker	3,4-dimethoxyphenylboronic acid	5.55 g, 30.48 mmol, 6 eq.	5 · Section B: Synthesis of OHPTP · Scheme S1
Base	K2CO3 solution	15 mL · 2 M	5 · Section B: Synthesis of OHPTP · Scheme S1
Additive	Tetrakis(triphenylphosphine)palladium(0)	175 mg, 152 umol, 0.03 eq.	5 · Section B: Synthesis of OHPTP · Scheme S1
Oxidant	Iron(III) chloride	2.60 g, 16.06 mmol, 10 eq.	5 · Section B: Synthesis of OHPTP · Scheme S1
Other	Boron tribromide solution in DCM	25.86 mL, 25.86 mmol, 18 eq. · 1 M	5 · Section B: Synthesis of OHPTP · Scheme S1

Complete recipeSource: SI

Route 4: Other

6 · Cu2(OHPTP) single crystal isolation

SolventsMeOH

Temperatureice bath during sonication

Time0.25

Work-upspin-coated onto Si substrates or drop-coated on TEM grids

Activationstarts from activated Cu2(OHPTP)

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated Cu2(OHPTP)	0.1 mg	6 · Cu2(OHPTP) single crystal isolation
Solvent	MeOH	1 mL	6 · Cu2(OHPTP) single crystal isolation