Synthesis · Growth mechanisms and anisotropic softness-dependent conductivity of orientation-controllable metal-organic framework nanofilms

11 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: SI

Route 1: Other

SI p002 · Preparation of Cu-BDC thin films

Metal precursorscopper acetate (1.0 mM in ethanol)

Linker precursors1,4-benzenedicarboxylic acid (BDC, 0.2 mM in ethanol)

Solventsethanol

Additivesfunctionalized substrate

Atmosphereambient/room temperature; drying atmosphere not specified

Temperatureroom temperature

Time10 s Cu immersion then 20 s BDC immersion per cycle; 10 cycles

Substrate orientationoriented thin film on substrate

Oxidant / reductantnone reported

Work-upethanol rinse between each step

Activationnone reported

Scalability contextDipping/immersion LPE-style cycle.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	1.0 mM	SI p002 · Preparation of Cu-BDC thin films
Linker	1,4-benzenedicarboxylic acid (BDC)	0.2 mM	SI p002 · Preparation of Cu-BDC thin films
Solvent	ethanol	Not specified	SI p002 · Preparation of Cu-BDC thin films

Complete recipeSource: SI

Route 2: Other

SI p002 · Preparation of Cu-BTC thin films

Metal precursorscopper acetate (1.0 mM in ethanol)

Linker precursors1,3,5-benzenetricarboxylate (BTC, 0.5 mM in ethanol)

Solventsethanol

Additives-NH2 functionalized substrates

Atmosphereambient/room temperature; drying atmosphere not specified

Temperatureroom temperature

Time3 min Cu immersion then 5 min BTC immersion per cycle; 10 cycles

Substrate orientation-NH2 functionalized substrate

Oxidant / reductantnone reported

Work-upethanol rinse between each step

Activationnone reported

Scalability contextDipping/immersion cycle adapted from Weckhuysen work.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	1.0 mM	SI p002 · Preparation of Cu-BTC thin films
Linker	1,3,5-benzenetricarboxylate (BTC)	0.5 mM	SI p002 · Preparation of Cu-BTC thin films
Solvent	ethanol	Not specified	SI p002 · Preparation of Cu-BTC thin films

Complete recipeSource: SI

Route 3: Solvothermal

SI p003 · Preparation of Cu-HHTP nanocrystals

Metal precursorscopper acetate (40 mg)

Linker precursorsHHTP (32.5 mg)

Solventsmethanol (28 mL; text typo 'methnol')

Additivesnone reported

Atmospheresealed glass bottle; dried under vacuum

Temperature65

Time24 h reaction after 15 min ultrasonication; 2 h vacuum drying

Substrate orientationnone

Oxidant / reductantnone reported

Work-upwash five times with methanol by dispersion and centrifugation at 4500 rpm for 10 min

Activationdried under vacuum at 65 C for 2 h

Scalability contextBatch nanocrystal synthesis in a 50 mL sealed glass bottle.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	40 mg	SI p003 · Preparation of Cu-HHTP nanocrystals
Linker	HHTP	32.5 mg	SI p003 · Preparation of Cu-HHTP nanocrystals
Solvent	methnol (MeOH) [sic]	28 mL	SI p003 · Preparation of Cu-HHTP nanocrystals

Partial recipeSource: Both

Route 4: Other

SI p002 · Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films

Metal precursorsas corresponding Cu-HHTP face-on or edge-on route

Linker precursorsas corresponding Cu-HHTP face-on or edge-on route

Solventsethanol

AdditivesCu-BDC or Cu-BTC bottom iMOF thin films as substrates

AtmosphereN2 drying for Cu-HHTP LbL steps

Temperatureroom temperature for Cu-HHTP LbL spraying

Timesame as face-on/edge-on Cu-HHTP routes; cycle count depends on upper layer

Substrate orientationCu-BDC or Cu-BTC thin film substrate

Oxidant / reductantnone reported

Work-upsame rinse/drying as Cu-HHTP LbL route

Activationnone reported

Scalability contextBottom iMOF significantly affects quality of the secondary cMOF film.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-BDC or Cu-BTC thin film substrate	Not specified	SI p002 · Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films
Metal Source	copper acetate	0.1 or 1.0 mM depending on Cu-HHTP route	SI p002 · Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films
Linker	HHTP	0.1, 1.0, or 2.0 mM depending on route	SI p002 · Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films

Complete recipeSource: Both

Route 5: Other

SI p002 · Preparation of edge-on Cu-HHTP thin films

Metal precursorscopper acetate (0.1 mM in ethanol)

Linker precursorsHHTP (0.5 mM in ethanol)

Solventsethanol; pure ethanol rinse

Additivesfunctionalized substrate

AtmosphereN2 drying after each step

Temperatureroom temperature for spraying

Time13 s Cu spray and 26 s HHTP spray per LbL cycle; x cycles

Substrate orientation-OH functionalized substrate; weak edge-on/a-b orientation observed

Oxidant / reductantnone reported

Work-uppure ethanol spray/rinse; N2 drying

Activationnone reported

Scalability contextUses 5x higher HHTP concentration than Cu0.1 P0.1 face-on route.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	0.1 mM	SI p002 · Preparation of edge-on Cu-HHTP thin films
Linker	HHTP	0.5 mM	SI p002 · Preparation of edge-on Cu-HHTP thin films
Solvent	ethanol	Not specified	SI p002 · Preparation of edge-on Cu-HHTP thin films

Complete recipeSource: Both

Route 6: Other

SI p002 · Preparation of edge-on Cu-HHTP thin films

Metal precursorscopper acetate (0.1 mM in ethanol)

Linker precursorsHHTP (1.0 mM in ethanol)

Solventsethanol; pure ethanol rinse

Additivesfunctionalized substrate

AtmosphereN2 drying after each step

Temperatureroom temperature for spraying

Time13 s Cu spray and 26 s HHTP spray per LbL cycle; x cycles

Substrate orientationedge-on/a-b oriented; c-axis parallel to substrate

Oxidant / reductantnone reported

Work-uppure ethanol spray/rinse; N2 drying

Activationnone reported

Scalability contextHigh ligand concentration supports stand-up packing and edge-on orientation.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	0.1 mM	SI p002 · Preparation of edge-on Cu-HHTP thin films
Linker	HHTP	1.0 mM	SI p002 · Preparation of edge-on Cu-HHTP thin films
Solvent	ethanol	Not specified	SI p002 · Preparation of edge-on Cu-HHTP thin films

Complete recipeSource: Both

Route 7: Other

SI p002 · Preparation of edge-on Cu-HHTP thin films

Metal precursorscopper acetate (0.1 mM in ethanol)

Linker precursorsHHTP (2.0 mM in ethanol)

Solventsethanol; pure ethanol rinse

Additivesfunctionalized substrate

AtmosphereN2 drying after each step

Temperatureroom temperature for spraying

Time13 s Cu spray and 26 s HHTP spray per LbL cycle; x cycles

Substrate orientationedge-on/a-b oriented; c-axis parallel to substrate

Oxidant / reductantnone reported

Work-uppure ethanol spray/rinse; N2 drying

Activationnone reported

Scalability context20x higher HHTP concentration than Cu0.1 P0.1 route; feeding rate about 173.1 molecules nm-2 s-1.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	0.1 mM	SI p002 · Preparation of edge-on Cu-HHTP thin films
Linker	HHTP	2.0 mM	SI p002 · Preparation of edge-on Cu-HHTP thin films
Solvent	ethanol	Not specified	SI p002 · Preparation of edge-on Cu-HHTP thin films

Complete recipeSource: Both

Route 8: Other

SI p002 · Preparation of face-on Cu-HHTP thin films

Metal precursorscopper acetate (0.1 mM in ethanol)

Linker precursorsHHTP (0.1 mM in ethanol)

Solventsethanol; pure ethanol rinse

Additivesfunctionalized substrate

AtmosphereN2 drying after each step

Temperatureroom temperature for spraying

Time20 s Cu spray and 40 s HHTP spray per LbL cycle; x cycles

Substrate orientation-OH functionalized substrate; face-on/c-oriented 2D planes

Oxidant / reductantnone reported

Work-uppure ethanol spray/rinse; N2 drying

Activationnone reported

Scalability contextReduced Cu concentration gives about 2 nm growth per cycle and improved orientation.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	0.1 mM	SI p002 · Preparation of face-on Cu-HHTP thin films
Linker	HHTP	0.1 mM	SI p002 · Preparation of face-on Cu-HHTP thin films
Solvent	ethanol	Not specified	SI p002 · Preparation of face-on Cu-HHTP thin films

Complete recipeSource: Both

Route 9: Other

SI p002 · Preparation of face-on Cu-HHTP thin films

Metal precursorscopper acetate (1.0 mM in ethanol)

Linker precursorsHHTP (0.1 mM in ethanol)

Solventsethanol; pure ethanol rinse

Additivesfunctionalized Si, Si/SiO2, glass, Cr/Au, or mica substrates depending on measurement

AtmosphereN2 drying after each step

Temperatureroom temperature for spraying; substrate functionalization includes Piranha at 100 C and optional 3-APTS at 50 C for 24 h

Time20 s Cu spray and 40 s HHTP spray per LbL cycle; x cycles

Substrate orientation-OH functionalized substrate; face-on/c-oriented 2D planes

Oxidant / reductantnone reported

Work-uppure ethanol spray/rinse to remove residual reactants; N2 drying each step

Activationnone reported

Scalability contextSpray LbL-LPE method gives controlled thickness increment and smooth surface.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	1.0 mM	SI p002 · Preparation of face-on Cu-HHTP thin films
Linker	HHTP (2,3,6,7,10,11-hexahydrotriphenylene)	0.1 mM	SI p002 · Preparation of face-on Cu-HHTP thin films
Solvent	ethanol	Not specified	SI p002 · Preparation of face-on Cu-HHTP thin films

Complete recipeSource: SI

Route 10: Other

p002-p003 · Materials and Methods; Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-BTC-10C thin film	Not specified	p002-p003 · Materials and Methods; Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films
Metal Source	copper(II) acetate in ethanol	1.0 mM	p002-p003 · Materials and Methods; Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films
Linker	HHTP (2,3,6,7,10,11-hexahydrotriphenylene) in ethanol	0.1 mM	p002-p003 · Materials and Methods; Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films
Solvent	ethanol	Not specified	p002-p003 · Materials and Methods; Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films
Other	nitrogen	Not specified	p002-p003 · Materials and Methods; Preparation of face-on/edge-on Cu-HHTP thin films on iMOF heterostructured thin films

Partial recipeSource: Both

Route 11: Other

p006 · Materials and Methods

Metal precursorsCu-BTC route precursors for top layer; Cu-HHTP/Cu-BTC bilayer substrate

Linker precursorsBTC for top iMOF layer

Solventsethanol

Additivesface-on Cu1.0 P0.1-40C-on-Cu-BTC thin film substrate

Atmospherenot specified beyond component routes

Temperatureroom temperature for Cu-BTC dipping

Timesimilar Cu-BTC route; exact details not restated

Substrate orientationMoM thin film substrate

Oxidant / reductantnone reported

Work-upethanol rinse between Cu-BTC steps by analogy

Activationnone reported

Scalability contextDemonstrates multilayered MoM construction.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	face-on Cu1.0 P.01-40C-on-Cu-BTC thin films	Not specified	p006 · Materials and Methods
Metal Source	copper acetate	1.0 mM by Cu-BTC route	p006 · Materials and Methods
Linker	BTC	0.5 mM by Cu-BTC route	p006 · Materials and Methods