Synthesis evidence

Stable organic radical stacked by in situ coordination to rare earth cations in MOF materials

Gandara F., Snejko N., Andres A.D. et al. · RSC Advances · 2012 · 949-955

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

p003 / journal p.951 · Results and discussions · Table 2

Metal precursorsCoCl2 or FeCl2
Linker precursorsNa2AQDS
Solventswater and n-BuOH, molar composition equivalent to optimised rare-earth mixture
Additivesnone reported
Atmospherenot specified
Temperature180
Time18
Oxidant / reductantnone; AQDS remains dianionic/non-radical
Work-upnot described
Activationnone reported
Scalability contextControl products show the same structural type but no radical formation.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCoCl2not reported · equivalent to optimised rare-earth mixturep003 / journal p.951 · Results and discussions · Table 2
Metal SourceFeCl2not reported · equivalent to optimised rare-earth mixturep003 / journal p.951 · Results and discussions · Table 2
LinkerNa2AQDSnot reported · equivalent to optimised rare-earth mixturep003 / journal p.951 · Results and discussions · Table 2
Solventwater/n-BuOHnot reported · equivalent to optimised rare-earth mixturep003 / journal p.951 · Results and discussions · Table 2
Complete recipeSource: Both

Route 2: Solvothermal

p001 / journal p.949 · Experimental section

Metal precursorsLa(NO3)3.6H2O (OCR in text appears as La(NO2)3.6H2O, but later control text and chemical context identify nitrate)
Linker precursorsNa2AQDS (anthraquinone-1,5-disulfonate disodium salt)
Solvents5.4 mL water; 16.4 mL n-BuOH
Additivesn-BuOH cosolvent; excess AQDS relative to Ln
Atmospheresealed Teflon-lined stainless steel autoclave; atmosphere not otherwise specified
Temperature180
Time18
Oxidant / reductantin situ reduction to semiquinone radical during solvothermal reaction; no separate reductant reported
Work-upcooled to room temperature; filtered; washed thoroughly with deionised water and acetone until filtrate colourless; dried in air
Activationnone reported
Scalability contextReported pure target phase in good yield, 60% on La basis, when AQDS/Ln = 2.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerNa2AQDS (Sigma-Aldrich, used as received)0.260 gp001 / journal p.949 · Experimental section
Metal SourceLa(NO3)3.6H2O / text OCR La(NO2)3.6H2O (Sigma-Aldrich, used as received)0.130 gp001 / journal p.949 · Experimental section
Solventwater5.4 mL · molar composition La3+:2AQDS:1000H2O:600n-BuOHp001 / journal p.949 · Experimental section
Solventn-BuOH16.4 mL · molar composition La3+:2AQDS:1000H2O:600n-BuOHp001 / journal p.949 · Experimental section
Partial recipeSource: Main

Route 3: Solvothermal

p003 / journal p.951 · Results and discussions

Metal precursorsnone
Linker precursorsNa2AQDS
Solventswater and n-BuOH, same amounts as target synthesis
Additivesnone reported
Atmospheresealed solvothermal vessel implied; not fully specified
Temperature180
Time18
Oxidant / reductantnone reported
Work-upnot described
Activationnone reported
Scalability contextControl gave large orange sodium AQDS crystals, not the radical RPF8 framework.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerNa2AQDSsame amount as target synthesisp003 / journal p.951 · Results and discussions
Solventwatersame amount as target synthesisp003 / journal p.951 · Results and discussions
Solventbutanolsame amount as target synthesisp003 / journal p.951 · Results and discussions
Complete recipeSource: Both

Route 4: Solvothermal

p001-p002 / journal pp.949-950 · Experimental section

Metal precursorshexahydrated rare-earth nitrate salts of Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er
Linker precursorsNa2AQDS
Solventswater and n-BuOH in the same molar composition as La-RPF8
Additivesn-BuOH cosolvent; AQDS/Ln = 2
Atmospheresealed Teflon-lined stainless steel autoclave; atmosphere not otherwise specified
Temperature180
Time18
Oxidant / reductantin situ semiquinone radical formation; no separate reductant reported
Work-upsame filtration, water/acetone washing and air drying as La-RPF8
Activationnone reported
Scalability contextSame molar composition as the La reaction; individual metal salt masses are not listed but are implied by stoichiometry.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerNa2AQDSsame molar composition as La-RPF8 · Ln3+:2AQDS:1000H2O:600n-BuOHp001-p002 / journal pp.949-950 · Experimental section
Metal SourcePr, Nd, Sm, Eu, Gd, Tb, Dy, Ho or Er hexahydrated nitrate saltcorresponding amount · Ln3+:2AQDS:1000H2O:600n-BuOHp001-p002 / journal pp.949-950 · Experimental section
Solventwatersame as La route by molar compositionp001-p002 / journal pp.949-950 · Experimental section
Solventn-BuOHsame as La route by molar compositionp001-p002 / journal pp.949-950 · Experimental section