Synthesis evidence

Application of two Cu(II)-azido based 1D coordination polymers in optoelectronic device: Structural characterization and experimental studies

Mondal M., Jana S., Drew M.G.B. et al. · Polymer · 2020 · 122815

4 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

p002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1

Metal precursorsCu(ClO4)2.6H2O (370 mg, 1 mmol) in 15 mL methanol
Linker precursorsHL1 methanolic solution prepared from 2-hydroxy-5-nitrobenzaldehyde and N,N-dimethyl-1,2-ethylenediamine followed by NaBH4 reduction and HCl acidification
SolventsMethanol and water; CH3OH-H2O mixed solvent about 10:1 v/v
AdditivesNaN3 aqueous solution; concentrated HCl used in ligand workup
AtmosphereOpen air for crystallisation; film drying atmosphere not applicable
Temperaturereflux; ligand solution cooled to 0 C during NaBH4 addition
Time1 h ligand reflux; 1 h complex reflux
Oxidant / reductantNaBH4 (210 mg, 6 mmol) for ligand reduction
Work-upAfter complex reflux, filtered; filtrate kept in open air; slow evaporation gave reddish needle crystals.
Scalability contextCaution in main text notes perchlorate and azide salts of metal complexes may be explosive and only small amounts should be prepared.
Show 8 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(ClO4)2.6H2O370 mg, 1 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
LinkerHL1 = 2-[(2-dimethylamino-ethylamino)-methyl]-4-nitrophenol1 mmol previously prepared methanolic solutionp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Other2-hydroxy-5-nitrobenzaldehyde835.6 mg, 5 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
OtherN,N-dimethyl-1,2-ethylenediamine0.55 mL, 5 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Reductantsodium borohydride210 mg, 6 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Acidconcentrated HCl5 mLp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
AdditiveNaN3130 mg, 2 mmol · aqueous solution in 5 mL waterp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Solventmethanol30 mL for ligand synthesis; 15 mL for Cu salt solutionp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Partial recipeSource: Main

Route 2: Other

p002-p003 · 2.6 Thin film fabrication from the precursor complexes

SolventsDMF dispersion; soap-water, distilled water, 1:1 NH3/isopropanol vapour cleaning
AtmosphereDried in inert atmosphere; stored in desiccators
Temperaturehot air oven drying temperature not specified
TimeITO sonicated 1 h; dried 2 h; complex dispersion ultrasonicated 1 h; spin 3 min at 600 rpm and 5 min at 1200 rpm
Substrate orientationITO coated glass, resistance about 10 ohm/sq cm, surface area 1.0 x 1.0 cm2
Work-upCleaned ITO, deposited dispersion at centre, spin-coated, dried under inert atmosphere and stored in desiccator.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Othercomplex 1about 3-4 mg · DMF ratio 1:4p002-p003 · 2.6 Thin film fabrication from the precursor complexes
SolventDMFcomplex:DMF ratio 1:4p002-p003 · 2.6 Thin film fabrication from the precursor complexes
OtherITO substrate1.0 x 1.0 cm2, resistance about 10 ohm/sq cmp002-p003 · 2.6 Thin film fabrication from the precursor complexes
Complete recipeSource: Main

Route 3: Other

p002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1

Metal precursorsCu(ClO4)2.6H2O (370 mg, 1 mmol) in 15 mL methanol
Linker precursorsHL2 methanolic solution prepared from 2-hydroxy-5-nitrobenzaldehyde and N,N-diethyl-1,2-ethylenediamine followed by NaBH4 reduction and HCl acidification
SolventsMethanol and water; CH3OH-H2O mixed solvent about 10:1 v/v
AdditivesNaN3 aqueous solution; concentrated HCl used in ligand workup
AtmosphereOpen air for crystallisation
Temperaturereflux; ligand solution cooled to 0 C during NaBH4 addition
Time1 h ligand reflux; 1 h complex reflux
Oxidant / reductantNaBH4 (210 mg, 6 mmol) for ligand reduction
Work-upSame procedure as complex 1 using HL2; filtration and slow evaporation of filtrate.
Scalability contextCaution in main text notes perchlorate and azide salts of metal complexes may be explosive and only small amounts should be prepared.
Show 8 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(ClO4)2.6H2O370 mg, 1 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
LinkerHL2 = 2-[(2-diethylamino-ethylamino)-methyl]-4-nitrophenol1 mmol previously prepared methanolic solutionp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Other2-hydroxy-5-nitrobenzaldehyde835.6 mg, 5 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
OtherN,N-diethyl-1,2-ethylenediamine0.70 mL, 5 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Reductantsodium borohydride210 mg, 6 mmolp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Acidconcentrated HCl5 mLp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
AdditiveNaN3130 mg, 2 mmol · aqueous solution in 5 mL waterp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Solventmethanol30 mL for ligand synthesis; 15 mL for Cu salt solutionp002 · 2.2 Synthesis of the ligands; 2.3 Syntheses of the complexes · Scheme 1
Partial recipeSource: Main

Route 4: Other

p002-p003 · 2.6 Thin film fabrication from the precursor complexes

SolventsDMF dispersion; soap-water, distilled water, 1:1 NH3/isopropanol vapour cleaning
AtmosphereDried in inert atmosphere; stored in desiccators
Temperaturehot air oven drying temperature not specified
TimeITO sonicated 1 h; dried 2 h; complex dispersion ultrasonicated 1 h; spin 3 min at 600 rpm and 5 min at 1200 rpm
Substrate orientationITO coated glass, resistance about 10 ohm/sq cm, surface area 1.0 x 1.0 cm2
Work-upCleaned ITO, deposited dispersion at centre, spin-coated, dried under inert atmosphere and stored in desiccator.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Othercomplex 2about 3-4 mg · DMF ratio 1:4p002-p003 · 2.6 Thin film fabrication from the precursor complexes
SolventDMFcomplex:DMF ratio 1:4p002-p003 · 2.6 Thin film fabrication from the precursor complexes
OtherITO substrate1.0 x 1.0 cm2, resistance about 10 ohm/sq cmp002-p003 · 2.6 Thin film fabrication from the precursor complexes