Synthesis · Two-Dimensional Conductive Metal-Organic Framework Reinforced Spinterface in Organic Spin Valves

9 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 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device

Metal precursorsLSMO target for bottom electrode; Co and Au evaporants for top electrode/protection layer.

Linker precursorsPcCu-Cu film prepared by LBL route.

SolventsChloroform cleaning for STO/STO-LSMO before film growth.

AtmosphereCo and Au deposited by thermal evaporation.

Substrate orientationSTO (001)

Work-upBottom LSMO electrode sputtering, PcCu-Cu LBL growth, Co/Au thermal evaporation.

Scalability contextJunction area 200 um x 200 um.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LSMO target/electrode	45 nm thick, 200 um wide	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device
Other	Co	top electrode	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device
Other	Au	protection layer	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device

Complete recipeSource: Both

Route 2: Other

S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device

Metal precursorsLSMO target for bottom electrode; Co and Au evaporants for top electrode/protection layer.

Linker precursorsPcH2-Cu film prepared by LBL route.

SolventsChloroform cleaning for STO/STO-LSMO before film growth.

AtmosphereCo and Au deposited by thermal evaporation.

Substrate orientationSTO (001)

Work-upBottom LSMO electrode sputtering, PcH2-Cu LBL growth, Co/Au thermal evaporation.

Scalability contextJunction area 200 um x 200 um.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LSMO target/electrode	45 nm thick, 200 um wide	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device
Other	Co	top electrode	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device
Other	Au	protection layer	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device

Complete recipeSource: Both

Route 3: Other

S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device

Metal precursorsLSMO target for bottom electrode; Co and Au evaporants for top electrode/protection layer.

Linker precursorsPcNi-Cu film prepared by LBL route.

SolventsChloroform cleaning for STO/STO-LSMO before film growth.

AtmosphereCo and Au deposited by thermal evaporation; high vacuum during Co deposition inferred from discussion.

Substrate orientationSTO (001)

Work-upBottom 45 nm, 200 um wide LSMO electrodes made by RF magnetron sputtering through shadow mask; PcNi-Cu grown on STO/LSMO; Co/Au thermally evaporated.

Scalability contextJunction area 200 um x 200 um.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	LSMO target/electrode	45 nm thick, 200 um wide	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device
Other	Co	top electrode; ~30 nm in cross-section sample	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device
Other	Au	protection layer; ~150 nm in cross-section sample	S5 · Fabrication of the LSMO/PcM-Cu (M = Ni, Cu, H2)/Co/Au Device

Complete recipeSource: Both

Route 4: Other

S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1

Metal precursors0.1 mM Cu(OAc)2 in ethanol.

Linker precursors0.01 mM PcCu-(OH)8 suspension in ethanol.

SolventsEthanol; substrate cleaning with deionized water, ethanol, acetone, isopropyl alcohol or chloroform depending on substrate.

AdditivesPiranha solution for glass hydroxylation; H2O/H2O2/NH3.H2O (1:1:5 v/v/v) for STO and STO/LSMO hydroxylation.

AtmosphereFilms dried in N2 stream after substrate cleaning; no special growth atmosphere reported.

Temperatureroom temperature for dipping; glass hydroxylation 100; STO/STO-LSMO hydroxylation 85

Time0.5 h substrate hydroxylation for STO/STO-LSMO; 1 h for glass piranha treatment; per-cycle soaking 10 min in Cu(OAc)2 and 20 min in linker.

Substrate orientationSTO (001) for device substrates; hydroxyl-terminated glass/STO/STO-LSMO.

Oxidant / reductantCu(OAc)2 participates in coordination/redox with ligand hydroxyl groups.

Work-upPure ethanol rinse after each metal and linker soak.

Scalability contextAutomatic dip-coating produced smooth, continuous, large-area films and centimetre-sized substrates.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	0.1 mM in ethanol	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Linker	PcCu-(OH)8	0.01 mM suspension in ethanol	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Solvent	ethanol	soaking and rinse solvent	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1

Complete recipeSource: SI

Route 5: Solvothermal

S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders

Metal precursorsCopper acetate, 3.0 mg, 15 umol; Cu present in PcCu-(OH)8 linker.

Linker precursorsPcCu-(OH)8, 5.3 mg, 7.5 umol.

SolventsDMF, water, acetone wash.

AdditivesAmmonium hydroxide solution (~25% v/v), 340 uL.

AtmosphereAutoclave sealed; no special gas atmosphere reported.

Temperature120

Time72

Oxidant / reductantCopper acetate acts as Cu source; redox between hydroxyl group and Cu ion inferred by XPS.

Work-upCool to room temperature; collect black solid by centrifugation; wash thoroughly with DMF, water, and acetone.

ActivationDried in vacuum for 12 h.

Scalability contextYield 73% based on PcCu-Cu MOF.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PcCu-(OH)8	5.3 mg, 7.5 umol	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Metal Source	copper acetate	3.0 mg, 15 umol · 0.5 mL DMF solution	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Solvent	N,N-dimethylformamide (DMF)	4 mL plus 0.5 mL metal-source solution	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Base	ammonium hydroxide solution	340 uL · ~25% v/v	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Solvent	water	4.5 mL	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders

Complete recipeSource: Both

Route 6: Other

S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1

Metal precursors0.1 mM Cu(OAc)2 in ethanol.

Linker precursors0.01 mM PcH2-(OH)8 suspension in ethanol.

SolventsEthanol; substrate cleaning with deionized water, ethanol, acetone, isopropyl alcohol or chloroform depending on substrate.

AdditivesPiranha solution for glass hydroxylation; H2O/H2O2/NH3.H2O (1:1:5 v/v/v) for STO and STO/LSMO hydroxylation.

AtmosphereFilms dried in N2 stream after substrate cleaning; no special growth atmosphere reported.

Temperatureroom temperature for dipping; glass hydroxylation 100; STO/STO-LSMO hydroxylation 85

Time0.5 h substrate hydroxylation for STO/STO-LSMO; 1 h for glass piranha treatment; per-cycle soaking 10 min in Cu(OAc)2 and 20 min in linker.

Substrate orientationSTO (001) for device substrates; hydroxyl-terminated glass/STO/STO-LSMO.

Oxidant / reductantCu(OAc)2 participates in coordination/redox with ligand hydroxyl groups.

Work-upPure ethanol rinse after each metal and linker soak.

Scalability contextAutomatic dip-coating produced smooth, continuous, large-area films and centimetre-sized substrates.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	0.1 mM in ethanol	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Linker	PcH2-(OH)8	0.01 mM suspension in ethanol	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Solvent	ethanol	soaking and rinse solvent	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1

Complete recipeSource: SI

Route 7: Solvothermal

S4-S5 · Synthesis of PcH2-Cu MOF powder

Metal precursorsCopper acetate, 4.8 mg, 24 umol.

Linker precursorsPcH2-(OH)8, 7.8 mg, 12 umol.

SolventsDMF, water, acetone wash.

AdditivesAmmonium hydroxide solution (~25% v/v), 530 uL.

AtmosphereAutoclave sealed; no special gas atmosphere reported.

Temperature120

Time120

Oxidant / reductantCopper acetate acts as Cu source; redox between hydroxyl group and Cu ion inferred by XPS.

Work-upCool to room temperature; collect black solid by centrifugation; wash thoroughly with DMF, water, and acetone.

ActivationDried in vacuum for 12 h.

Scalability contextYield 83% based on PcH2-Cu MOF.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PcH2-(OH)8	7.8 mg, 12 umol	S4-S5 · Synthesis of PcH2-Cu MOF powder
Metal Source	copper acetate	4.8 mg, 24 umol · 0.8 mL DMF solution	S4-S5 · Synthesis of PcH2-Cu MOF powder
Solvent	N,N-dimethylformamide (DMF)	6.7 mL plus 0.8 mL metal-source solution	S4-S5 · Synthesis of PcH2-Cu MOF powder
Base	ammonium hydroxide solution	530 uL · ~25% v/v	S4-S5 · Synthesis of PcH2-Cu MOF powder
Solvent	water	2.5 mL	S4-S5 · Synthesis of PcH2-Cu MOF powder

Complete recipeSource: Both

Route 8: Other

S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1

Metal precursors0.1 mM Cu(OAc)2 in ethanol.

Linker precursors0.01 mM PcNi-(OH)8 suspension in ethanol.

SolventsEthanol; substrate cleaning with deionized water, ethanol, acetone, isopropyl alcohol or chloroform depending on substrate.

AdditivesPiranha solution for glass hydroxylation; H2O/H2O2/NH3.H2O (1:1:5 v/v/v) for STO and STO/LSMO hydroxylation.

AtmosphereFilms dried in N2 stream after substrate cleaning; no special growth atmosphere reported.

Temperatureroom temperature for dipping; glass hydroxylation 100; STO/STO-LSMO hydroxylation 85

Time0.5 h substrate hydroxylation for STO/STO-LSMO; 1 h for glass piranha treatment; per-cycle soaking 10 min in Cu(OAc)2 and 20 min in linker.

Substrate orientationSTO (001) for device substrates; hydroxyl-terminated glass/STO/STO-LSMO.

Oxidant / reductantCu(OAc)2 participates in coordination/redox with ligand hydroxyl groups.

Work-upPure ethanol rinse after each metal and linker soak; final rinse with deionized water/ethanol and N2 drying after substrate cleaning.

Scalability contextAutomatic dip-coating produced smooth, continuous, large-area films and centimetre-sized substrates.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	0.1 mM in ethanol	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Linker	PcNi-(OH)8	0.01 mM suspension in ethanol	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Solvent	ethanol	soaking and rinse solvent	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Oxidant	H2O2	in H2O/H2O2/NH3.H2O = 1:1:5	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1
Base	NH3.H2O	in H2O/H2O2/NH3.H2O = 1:1:5	S5 · Synthesis of PcM-Cu (M = Ni, Cu, H2) MOF film · Figure S1

Complete recipeSource: SI

Route 9: Solvothermal

S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders

Metal precursorsCopper acetate, 3.0 mg, 15 umol; Ni present in PcNi-(OH)8 linker.

Linker precursorsPcNi-(OH)8, 5.3 mg, 7.5 umol.

SolventsDMF, water, acetone wash.

AdditivesAmmonium hydroxide solution (~25% v/v), 340 uL.

AtmosphereAutoclave sealed; no special gas atmosphere reported.

Temperature120

Time72

Oxidant / reductantCopper acetate acts as Cu source; redox between hydroxyl group and Cu ion inferred by XPS.

Work-upCool to room temperature; collect black solid by centrifugation; wash thoroughly with DMF, water, and acetone.

ActivationDried in vacuum for 12 h.

Scalability contextYield ~88% based on PcNi-Cu MOF.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PcNi-(OH)8	5.3 mg, 7.5 umol	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Metal Source	copper acetate	3.0 mg, 15 umol · 0.5 mL DMF solution	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Solvent	N,N-dimethylformamide (DMF)	4 mL plus 0.5 mL metal-source solution	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Base	ammonium hydroxide solution	340 uL · ~25% v/v	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders
Solvent	water	4.5 mL	S4 · Synthesis of PcM-Cu (M = Ni, Cu) MOF powders