Synthesis · Controlling Film Formation and Host-Guest Interactions to Enhance the Thermoelectric Properties of Nickel-Nitrogen-Based 2D Conjugated Coordination Polymers

5 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Air Liquid Interface

p008 · Experimental Section - Synthesis

Metal precursorsNi(acac)2 in degassed DI water, 2.5 mmol L-1, 2-6 equiv.

Linker precursorsorganic ligand in DI water, 1.8 mmol L-1, 0.5 mL, 1 equiv.; HAB.3HCl for Ni-HAB

SolventsH2O / DI water; CHCl3 post-transfer soak

Additives25-times diluted 28% NH3 in H2O, 25-100 equiv.

Atmosphereset up in nitrogen-filled glovebox; non-airtight sealed vial transferred to ambient air for slow air diffusion

TemperatureNi(acac)2 dissolved at 60 C; components added at about 30 C; reaction kept at 45 C

Time12-15 h overnight

Substrate orientationfilms formed at air-liquid interface then transferred to O2-plasma-treated substrates in air

Oxidant / reductantambient O2/air as slow oxidant for oxidative dehydrogenation

Work-upthin films fully dried, soaked again in CHCl3 for a couple of minutes, and checked optically; air/yellow-light exposure during transfer typically 1-1.5 h

ActivationN2 storage overnight or annealing at 125 C for 90 min used as degassing treatments for transport samples; Ni-HAB also reported annealed in N2

Scalability context20 mL vial, water-based air-liquid interface method; authors describe it as generally applicable to four Ni-N cCP films.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(acac)2	0.72-2.16 mL, i.e. 2-6 equiv. · 2.5 mmol L-1	p008 · Experimental Section - Synthesis
Linker	HAB.3HCl	0.5 mL, 1 equiv. · 1.8 mmol L-1	p008 · Experimental Section - Synthesis
Base	28% NH3 in H2O diluted 25 times	25-100 equiv.	p008 · Experimental Section - Synthesis
Solvent	H2O / DI water	6 mL plus aqueous reagent solutions	p008 · Experimental Section - Synthesis
Oxidant	ambient O2 from air diffusion	slow diffusion through non-airtight cap	p008 · Experimental Section - Synthesis
Solvent	CHCl3	soak for a couple of minutes	p008 · Experimental Section - Synthesis

Complete recipeSource: SI

Route 2: Air Liquid Interface

p008 · Synthesis · Table S1

Metal precursorsNiCl2, Ni(OAc)2, or Ni(acac)2; 1.5-6 equiv. depending on screen

Linker precursorsHAB linker, 1 equiv. implied by model reaction

Solventsaqueous reaction media; optional DMF co-solvent in Figure S3

Additivesethylenediamine, NaOAc, NH3.H2O, or DBU bases

Atmospherenitrogen setup then ambient air diffusion unless control experiment stated otherwise

Temperature45 C

Timeovernight; control tests include 19 h glovebox and 15 h tight-cap air transfer

Substrate orientationfilms formed on solution surface where successful

Oxidant / reductantO2 diffusion from air; oxidation is necessary for film formation

Work-upfilm transfer and microscopy for successful films; powders or no product in unsuccessful screens

Activationnot generally applied in screen; annealing reported for optimized NH3.H2O condition

Scalability contextTable S1 records 11 screened condition sets.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	NiCl2; Ni(OAc)2; Ni(acac)2	1.5-6 equiv.	p008 · Synthesis · Table S1
Base	ethylenediamine; NaOAc; NH3.H2O; DBU	6 to >100 equiv. depending on row	p008 · Synthesis · Table S1
Linker	HAB	1 equiv. implied by synthesis	p008 · Synthesis · Table S1

Partial recipeSource: Both

Route 3: Air Liquid Interface

p008 · Experimental Section - Materials

Metal precursorsNi(acac)2 in degassed DI water, 2.5 mmol L-1

Linker precursorsHATI-H.6HCl; organic ligand solution 1.8 mmol L-1, 0.5 mL, 1 equiv.

SolventsH2O / DI water; CHCl3 post-transfer soak

Additives25-times diluted NH3 in H2O / NH4OH

Atmospherenitrogen-filled glovebox setup, then non-airtight sealed ambient-air diffusion

Temperature45 C reaction; about 30 C mixing

Time12-15 h overnight

Substrate orientationair-liquid interface film transferred to O2 plasma-treated substrates

Oxidant / reductantambient O2 as oxidant

Work-updry, CHCl3 soak, optical inspection

ActivationN2 storage overnight or annealing at 125 C for 90 min

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(acac)2	2-6 equiv. depending on reaction · 2.5 mmol L-1	p008 · Experimental Section - Materials
Linker	HATI-H.6HCl	1 equiv. · 1.8 mmol L-1	p008 · Experimental Section - Materials
Base	NH3.H2O / NH4OH	25-100 equiv. · 28% NH3 in H2O diluted 25 times	p008 · Experimental Section - Materials

Partial recipeSource: Both

Route 4: Air Liquid Interface

p008 · Experimental Section - Materials

Metal precursorsNi(acac)2 in degassed DI water, 2.5 mmol L-1

Linker precursorsHATI-Me.6HCl; organic ligand solution 1.8 mmol L-1, 0.5 mL, 1 equiv.

SolventsH2O / DI water; CHCl3 post-transfer soak

Additives25-times diluted NH3 in H2O / NH4OH

Atmospherenitrogen-filled glovebox setup, then non-airtight sealed ambient-air diffusion

Temperature45 C reaction; about 30 C mixing

Time12-15 h overnight

Substrate orientationair-liquid interface film transferred to O2 plasma-treated substrates

Oxidant / reductantambient O2 as oxidant

Work-updry, CHCl3 soak, optical inspection

ActivationN2 storage overnight or annealing at 125 C for 90 min

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(acac)2	2-6 equiv. depending on reaction · 2.5 mmol L-1	p008 · Experimental Section - Materials
Linker	HATI-Me.6HCl	1 equiv. · 1.8 mmol L-1	p008 · Experimental Section - Materials
Base	NH3.H2O / NH4OH	25-100 equiv. · 28% NH3 in H2O diluted 25 times	p008 · Experimental Section - Materials

Complete recipeSource: Both

Route 5: Air Liquid Interface

p004 · Synthesis and Characterizations · Figure 1a

Metal precursorsNi(acac)2 in degassed DI water, 2.5 mmol L-1

Linker precursorsHATP.6HCl; organic ligand solution 1.8 mmol L-1, 0.5 mL, 1 equiv.

SolventsH2O / DI water; CHCl3 post-transfer soak

Additives25-times diluted NH3 in H2O / NH4OH

Atmospherenitrogen-filled glovebox setup, then non-airtight sealed ambient-air diffusion

Temperature45 C reaction; about 30 C mixing

Time12-15 h overnight

Substrate orientationair-liquid interface film transferred to O2 plasma-treated substrates

Oxidant / reductantambient O2 as oxidant

Work-updry, CHCl3 soak, optical inspection

ActivationN2 storage overnight or annealing at 125 C for 90 min; high-vacuum annealing before temperature-dependent transport

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(acac)2	2-6 equiv. depending on reaction · 2.5 mmol L-1	p004 · Synthesis and Characterizations · Figure 1a
Linker	HATP.6HCl	1 equiv. · 1.8 mmol L-1	p004 · Synthesis and Characterizations · Figure 1a
Base	NH3.H2O / NH4OH	25-100 equiv. · 28% NH3 in H2O diluted 25 times	p004 · Synthesis and Characterizations · Figure 1a