Synthesis evidence

Semiconducting Manganese-Bipyridyl Coordination Polymer via a Manganese-Metal-Nanoparticle Approach

Reiss A., Gottlicher J., Vitova T. et al. · Inorganic Chemistry · 2025 · 9469-9476

2 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

6 · Experimental Section - Mn(0) Nanoparticles · Figure 1a,b

Metal precursorsMnCl2 (64.3 mg, 0.67 mmol)
Solvents1,2-dimethoxyethane (DME, 15 mL); toluene/THF 1:1 mixture for purification
AdditivesSodium metal (30.8 mg, 1.34 mmol); naphthalene (180.0 mg, 1.4 mmol)
AtmosphereDried argon atmosphere; Schlenk/glovebox handling; glassware evacuated, heated and flashed with argon three times
Temperature25
Time12
Oxidant / reductantIn situ sodium naphthalenide [NaNaph] reduces MnCl2 to Mn(0)
Work-upCentrifugation to separate nanoparticles; repeated redispersion/centrifugation at 25,000 rpm, 55,200 x g in/from 15 mL 1:1 toluene/THF.
ActivationOptional drying in vacuum (10^-3 mbar, 15 min) to obtain powder samples.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceMnCl264.3 mg (0.67 mmol)6 · Experimental Section - Mn(0) Nanoparticles · Figure 1a,b
Reductantsodium metal30.8 mg (1.34 mmol)6 · Experimental Section - Mn(0) Nanoparticles · Figure 1a,b
Additivenaphthalene180.0 mg (1.4 mmol)6 · Experimental Section - Mn(0) Nanoparticles · Figure 1a,b
Solvent1,2-dimethoxyethane (DME)15 mL6 · Experimental Section - Mn(0) Nanoparticles · Figure 1a,b
Solventtoluene/THF 1:1 mixture15 mL6 · Experimental Section - Mn(0) Nanoparticles · Figure 1a,b
Complete recipeSource: Main

Route 2: Other

6 · Experimental Section - [Na2Mn2(4,4'-bipy)7(2,2'-bipy)4] (1) · Figure 1c

Metal precursorsDried Mn(0) nanoparticles (36.9 mg, 0.60 mmol, prepared via [NaNaph]-driven reduction); residual/added NaCl available from nanoparticle synthesis
Linker precursors2,2'-bipyridine (93.7 mg, 0.60 mmol); 4,4'-bipyridine (164.0 mg, 1.05 mmol)
SolventsToluene (0.5 mL reaction solvent; 5 mL toluene wash during purification)
AdditivesNaCl from the Mn(0) nanoparticle synthesis is retained to form 1
AtmosphereDried argon atmosphere; sealed glass ampule
Temperature80
Time168
Oxidant / reductantLiquid-phase redox reaction of highly reactive Mn(0) nanoparticles with bipyridines; controlled oxidation in toluene
Work-upNatural cooling; add 5 mL toluene, short stirring, decant supernatant to remove unreacted Mn(0) nanoparticles and bipyridine; repeat until supernatant clear; manually separate crystals from NaCl and rinse with toluene.
Scalability contextLeaving NaCl in the reaction mixture allowed large quantities of 1 and gave about 80% yield relative to bipyridines; partial NaCl removal in the first observation gave only about 20% yield.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcedried Mn(0) nanoparticles36.9 mg (0.60 mmol)6 · Experimental Section - [Na2Mn2(4,4'-bipy)7(2,2'-bipy)4] (1) · Figure 1c
Linker2,2'-bipyridine (2,2'-bipy)93.7 mg (0.60 mmol)6 · Experimental Section - [Na2Mn2(4,4'-bipy)7(2,2'-bipy)4] (1) · Figure 1c
Linker4,4'-bipyridine (4,4'-bipy)164.0 mg (1.05 mmol)6 · Experimental Section - [Na2Mn2(4,4'-bipy)7(2,2'-bipy)4] (1) · Figure 1c
Solventtoluene0.5 mL reaction solvent; 5 mL purification wash6 · Experimental Section - [Na2Mn2(4,4'-bipy)7(2,2'-bipy)4] (1) · Figure 1c
AdditiveNaClnot quantified; originates from [NaNaph]/MnCl2 nanoparticle synthesis6 · Experimental Section - [Na2Mn2(4,4'-bipy)7(2,2'-bipy)4] (1) · Figure 1c