Synthesis · Enhancing Near-Infrared Photothermal Performance by Molecular Aggregation Optimization in Semiconductive Coordination Polymers

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

22503 · 2.1.1 Synthesis of Compound 1 · Figure S21a

Metal precursorsCdCl2.2.5H2O replacing Cd(NO3)2.4H2O

Linker precursorsH2ONDI (15 mg, 0.05 mmol); oxalic acid dihydrate (6.5 mg, 0.05 mmol)

Solvents2 mL DMF, 3 mL H2O

Additives1 mL 1 M HCl

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperature110

Time48

Work-upAllowed to cool to room temperature at 10 C/h; pure product verified by PXRD.

Scalability contextProduct weight 9.4 mg; yield 30%.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CdCl2.2.5H2O	not restated; replacement for Cd(NO3)2.4H2O	22503 · 2.1.1 Synthesis of Compound 1 · Figure S21a
Linker	H2ONDI	15 mg, 0.05 mmol	22503 · 2.1.1 Synthesis of Compound 1 · Figure S21a
Additive	oxalic acid dihydrate	6.5 mg, 0.05 mmol	22503 · 2.1.1 Synthesis of Compound 1 · Figure S21a
Solvent	DMF	2 mL	22503 · 2.1.1 Synthesis of Compound 1 · Figure S21a
Solvent	H2O	3 mL	22503 · 2.1.1 Synthesis of Compound 1 · Figure S21a
Acid	HCl	1 mL · 1 M	22503 · 2.1.1 Synthesis of Compound 1 · Figure S21a

Complete recipeSource: Main

Route 2: Solvothermal

22503 · 2.1.1 Synthesis of Compound 1

Metal precursorsCd(NO3)2.4H2O (30 mg, 0.1 mmol)

Linker precursorsH2ONDI (15 mg, 0.05 mmol); oxalic acid dihydrate (6.5 mg, 0.05 mmol)

Solvents2 mL DMF, 3 mL H2O

Additives1 mL 1 M HCl

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperature110

Time48

Work-upAllowed to cool to room temperature at 10 C/h; brown plate crystals obtained.

Scalability contextSmall-batch solvothermal reaction; yield not assigned specifically to the nitrate-crystal route.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cd(NO3)2.4H2O	30 mg, 0.1 mmol	22503 · 2.1.1 Synthesis of Compound 1
Linker	H2ONDI	15 mg, 0.05 mmol	22503 · 2.1.1 Synthesis of Compound 1
Additive	oxalic acid dihydrate	6.5 mg, 0.05 mmol	22503 · 2.1.1 Synthesis of Compound 1
Solvent	DMF	2 mL	22503 · 2.1.1 Synthesis of Compound 1
Solvent	H2O	3 mL	22503 · 2.1.1 Synthesis of Compound 1
Acid	HCl	1 mL · 1 M	22503 · 2.1.1 Synthesis of Compound 1

Complete recipeSource: Main

Route 3: Solvothermal

22503 · 2.1.3 Synthesis of Microcrystalline 2

Metal precursorsBa(NO3)2 (13 mg, 0.05 mmol)

Linker precursorsH2ONDI (15 mg, 0.05 mmol)

Solvents1.5 mL DMF, 3 mL H2O

Additives2,5-dihydroxy-1,4-benzoquinone (7 mg, 0.05 mmol)

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperature120

Time72

Oxidant / reductant2,5-dihydroxy-1,4-benzoquinone additive

Work-upCloudy suspensions removed; brown crystalline products suspended in DMF and briefly sonicated; process repeated several times.

Scalability contextProduct weight 9.5 mg; yield 40%.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ba(NO3)2	13 mg, 0.05 mmol	22503 · 2.1.3 Synthesis of Microcrystalline 2
Linker	H2ONDI	15 mg, 0.05 mmol	22503 · 2.1.3 Synthesis of Microcrystalline 2
Additive	2,5-dihydroxy-1,4-benzoquinone	7 mg, 0.05 mmol	22503 · 2.1.3 Synthesis of Microcrystalline 2
Solvent	DMF	1.5 mL	22503 · 2.1.3 Synthesis of Microcrystalline 2
Solvent	H2O	3 mL	22503 · 2.1.3 Synthesis of Microcrystalline 2

Complete recipeSource: Main

Route 4: Solvothermal

22503 · 2.1.2 Synthesis of Single Crystals of Compound 2

Metal precursorsBaCl2.2H2O (12 mg, 0.05 mmol)

Linker precursorsH2ONDI (15 mg, 0.05 mmol)

Solvents3 mL DMF, 1.5 mL H2O

Additives0.5 mL 1 M HCl

Atmospheresealed Teflon-lined autoclave; atmosphere not otherwise specified

Temperature120

Time48

Work-upAllowed to cool to 30 C at 10 C/h; brown crystals plus byproduct crystals obtained.

Scalability contextByproduct crystals prevented broader characterisation from this route.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	BaCl2.2H2O	12 mg, 0.05 mmol	22503 · 2.1.2 Synthesis of Single Crystals of Compound 2
Linker	H2ONDI	15 mg, 0.05 mmol	22503 · 2.1.2 Synthesis of Single Crystals of Compound 2
Solvent	DMF	3 mL	22503 · 2.1.2 Synthesis of Single Crystals of Compound 2
Solvent	H2O	1.5 mL	22503 · 2.1.2 Synthesis of Single Crystals of Compound 2
Acid	HCl	0.5 mL · 1 M	22503 · 2.1.2 Synthesis of Single Crystals of Compound 2