Synthesis evidence

Proton Conductive Metal-Organic Framework Encapsulating Emissive Hexacyanidochromate(III) Ions for Ratiometric and Lifetime-Based Detection of Humidity and Temperature

Niemiec M., Zakrzewski J.J., Reczynski M. et al. · Advanced Optical Materials · 2025 · 2403564

5 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

S3 · Synthesis of 1 and preparation of its air-dried form, 1a

Metal precursorsSrII(NO3)2 (0.05 mmol, 10.6 mg); (bmba)3[CrIII(CN)6] (0.05 mmol, 44.2 mg)
Linker precursors4,4'-bpdo (0.05 mmol, 18.8 mg)
Solvents0.25 mL H2O + 1 mL MeOH for Sr/linker; 2 mL MeOH for Cr precursor; methanol and diethyl ether washes
Additivesbis(alpha-methylbenzyl)amine cation present in precursor salt; no template reported in final framework
Atmosphereclosed vial stored in dark; drying in air under ambient laboratory conditions
Temperature21
Timenot specified for crystallisation; longer standing under ambient conditions for mass stabilisation
Work-upcrystals collected by suction filtration, washed with small portions of methanol and diethyl ether, left to dry in air
Activationambient air drying to 1a; no thermal activation for 1a
Scalability contextYield 16.4 mg (10.4%) based on SrII(NO3)2 for 1a.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceSrII(NO3)20.05 mmol (10.6 mg)S3 · Synthesis of 1 and preparation of its air-dried form, 1a
Linker4,4'-bpdo0.05 mmol (18.8 mg)S3 · Synthesis of 1 and preparation of its air-dried form, 1a
Other(bmba)3[CrIII(CN)6]0.05 mmol (44.2 mg)S3 · Synthesis of 1 and preparation of its air-dried form, 1a
SolventH2O0.25 mLS3 · Synthesis of 1 and preparation of its air-dried form, 1a
Solventmethanol1 mL + 2 mLS3 · Synthesis of 1 and preparation of its air-dried form, 1a
Solventdiethyl ether washsmall portionsS3 · Synthesis of 1 and preparation of its air-dried form, 1a
Complete recipeSource: SI

Route 2: Other

S3 · Preparation of 1deh

Metal precursorsair-stable 1a bulk sample
Linker precursorsretained 4,4'-bpdo framework from 1a
Solventsnone added; vacuum removal of crystallisation water
Atmospherevacuum with repeated Ar purging; glovebox Ar handling
Temperature60
Time24
Work-upsealed/handled in glovebox; P-XRD sample sealed in glass capillary
Activationthermal/vacuum dehydration to solvent-free 1deh
Scalability contextBulk powder preparation reported for optical studies; single-crystal dehydration for SC-XRD used 80 C after staged heating.
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
Otherair-stable 1abulk sample; amount not reportedS3 · Preparation of 1deh
Partial recipeSource: SI

Route 3: Other

S4 · Synthesis of 2, 3, and 4

Metal precursorsSrII(NO3)2 (0.05 mmol, 10.6 mg); (bmba)3[CoIII(CN)6] (0.05 mmol, 44.6 mg)
Linker precursors4,4'-bpdo (0.05 mmol, 18.8 mg)
Solventsanalogous to 1: H2O/MeOH; methanol and diethyl ether washes
Additivesbis(alpha-methylbenzyl)amine cation present in precursor salt
Atmosphereclosed vial, dark; air drying
Temperature21
Timenot specified
Work-upair-dried phase 2a prepared analogously to 1a; CHN/TG confirmed composition
Activationambient air drying
Scalability contextYield 17.3 mg (11.0%) based on Sr(NO3)2.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceSrII(NO3)20.05 mmol (10.6 mg inferred from route 1)S4 · Synthesis of 2, 3, and 4
Linker4,4'-bpdo0.05 mmol (18.8 mg inferred from route 1)S4 · Synthesis of 2, 3, and 4
Other(bmba)3[CoIII(CN)6]0.05 mmol (44.6 mg)S4 · Synthesis of 2, 3, and 4
Partial recipeSource: SI

Route 4: Other

S4 · Synthesis of 2, 3, and 4

Metal precursorsBaII(NO3)2 (0.05 mmol, 13.1 mg); (bmba)3[CrIII(CN)6] (0.05 mmol, 44.2 mg)
Linker precursors4,4'-bpdo (0.05 mmol, 18.8 mg inferred from route 1)
Solventsanalogous to 1: H2O/MeOH; methanol and diethyl ether washes
Additivesbis(alpha-methylbenzyl)amine cation present in precursor salt
Atmosphereclosed vial, dark; air drying
Temperature21
Timenot specified
Work-upsingle crystals taken from mother solution; air-dried phase 3a used for further physical experiments
Activationambient air drying
Scalability contextYield 20.4 mg (15.5%) based on Ba(NO3)2.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceBaII(NO3)20.05 mmol (13.1 mg)S4 · Synthesis of 2, 3, and 4
Linker4,4'-bpdo0.05 mmol (18.8 mg inferred)S4 · Synthesis of 2, 3, and 4
Other(bmba)3[CrIII(CN)6]0.05 mmol (44.2 mg)S4 · Synthesis of 2, 3, and 4
Partial recipeSource: SI

Route 5: Other

S4 · Synthesis of 2, 3, and 4

Metal precursorsBaII(NO3)2 (0.05 mmol, 13.1 mg); (bmba)3[CoIII(CN)6] (0.05 mmol, 44.6 mg)
Linker precursors4,4'-bpdo (0.05 mmol, 18.8 mg inferred from route 1)
Solventsanalogous to 1: H2O/MeOH; methanol and diethyl ether washes
Additivesbis(alpha-methylbenzyl)amine cation present in precursor salt
Atmosphereclosed vial, dark; air drying
Temperature21
Timenot specified
Work-upsingle crystals taken from mother solution; air-dried phase 4a used for further physical experiments
Activationambient air drying
Scalability contextYield 19.2 mg (14.7%) based on Ba(NO3)2.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceBaII(NO3)20.05 mmol (13.1 mg)S4 · Synthesis of 2, 3, and 4
Linker4,4'-bpdo0.05 mmol (18.8 mg inferred)S4 · Synthesis of 2, 3, and 4
Other(bmba)3[CoIII(CN)6]0.05 mmol (44.6 mg)S4 · Synthesis of 2, 3, and 4