cMOF Evidence Base

Synthesis evidence

Semiconducting Supramolecular Organic Frameworks Assembled from a Near-Infrared Fluorescent Macrocyclic Probe and Fullerenes

Kaur R., Sen S., Larsen M.C. et al. · Journal of the American Chemical Society · 2020 · 11497-11505

3 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

S5-S8 · Synthesis, NMR and MALDI-TOF-MS analyses for the compounds · Scheme S1

Metal precursorsZn(OAc)2 used transiently in compound 7; final receptor 2 is demetalated/metal-free
Linker precursorsdipyrromethane; 3-trimethylsilylethynylbenzaldehyde; phosphine 3; compounds 4-8
SolventsCH2Cl2, CHCl3, CH3COOH, THF, toluene, MeOH, petroleum ether, methanolic TFA; THF for final preparative GPC
AdditivesTFA, chloranil, NEt3, PbO2, NaHMDS, NH4Cl, Zn(OAc)2, K2CO3, CuCl, TMEDA, 4,4'-bipyridyl
AtmosphereAr for compound 4; dry air for final Glaser-Hay coupling to receptor 2
Temperatureambient/room temperature for final coupling; -78 C to ambient for compound 6; 70 C reflux for compound 7
Time24 h final coupling; precursor steps include 24 h, 5-6 h, 5 h at -78 C plus 18 h, 1 h, and 48 h
Oxidant / reductantchloranil; PbO2; CuCl/dry air Glaser-Hay coupling; TFA demetalation
Work-upWater washes, drying over anhydrous MgSO4, solvent removal under reduced pressure, alumina/silica chromatography and recycling preparative GPC.
Scalability contextFinal receptor 2 isolated in 22% overall yield from compound 8; multiple chromatography/GPC purification steps imply small-scale molecular synthesis.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Linker80.04 mmol, 0.043 gmS5-S8 · Synthesis, NMR and MALDI-TOF-MS analyses for the compounds · Scheme S1
Solventanhydrous dichloromethane300 mLS5-S8 · Synthesis, NMR and MALDI-TOF-MS analyses for the compounds · Scheme S1
AdditiveCuCl4 mmol, 0.40 gmS5-S8 · Synthesis, NMR and MALDI-TOF-MS analyses for the compounds · Scheme S1
AdditiveTMEDA4 mmol, 0.6 mLS5-S8 · Synthesis, NMR and MALDI-TOF-MS analyses for the compounds · Scheme S1
Additive4,4'-bipyridyl0.3 mmol, 0.047 gmS5-S8 · Synthesis, NMR and MALDI-TOF-MS analyses for the compounds · Scheme S1
Acidmethanolic TFANot specifiedS5-S8 · Synthesis, NMR and MALDI-TOF-MS analyses for the compounds · Scheme S1
Partial recipeSource: SI

Route 2: Other

S21 · Single crystal X-ray structure of the supramolecular complex of 2 with C60 · Table S2

Metal precursorsNone
Linker precursorsreceptor 2 and C60
Solventstoluene solution; hexanes anti-solvent
Atmospherenot specified
Temperatureroom temperature implied; data collection at 100 K
Work-upCrystals cut from larger crystal for X-ray analysis; no activation reported.
Scalability contextSingle crystals were fragile and dimensions limited reliable anisotropic conductivity estimates.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Linkerreceptor 2Not specifiedS21 · Single crystal X-ray structure of the supramolecular complex of 2 with C60 · Table S2
OtherC60Not specifiedS21 · Single crystal X-ray structure of the supramolecular complex of 2 with C60 · Table S2
SolventtolueneNot specifiedS21 · Single crystal X-ray structure of the supramolecular complex of 2 with C60 · Table S2
SolventhexanesNot specifiedS21 · Single crystal X-ray structure of the supramolecular complex of 2 with C60 · Table S2
Partial recipeSource: SI

Route 3: Other

S24 · Single crystal X-ray structure of the supramolecular complex of 2 with C70 · Table S3

Metal precursorsNone
Linker precursorsreceptor 2 and C70
Solventstoluene solution; diisopropyl ether anti-solvent
Atmospherenot specified
Temperatureroom temperature
Timeapproximately 72 h
Work-upCrystals cut from larger crystal for X-ray analysis; no activation reported.
Scalability contextSingle crystals were fragile and dimensions limited reliable perpendicular-axis conductivity estimates.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Linkerreceptor 2Not specifiedS24 · Single crystal X-ray structure of the supramolecular complex of 2 with C70 · Table S3
OtherC70Not specifiedS24 · Single crystal X-ray structure of the supramolecular complex of 2 with C70 · Table S3
SolventtolueneNot specifiedS24 · Single crystal X-ray structure of the supramolecular complex of 2 with C70 · Table S3
Solventdiisopropyl etherNot specifiedS24 · Single crystal X-ray structure of the supramolecular complex of 2 with C70 · Table S3