Synthesis · Microscopic Insights into Cation-Coupled Electron Hopping Transport in a Metal-Organic Framework

3 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

2 · General Materials and Experimental Methods

Metal precursorsnone

Linker precursors1,4,5,8-naphthalenetetracarboxylic dianhydride; 4-amino-3-hydroxy benzoic acid

Solventsanhydrous DMF; HCl/H2O precipitation; EtOH, H2O and Et2O washes

Additives1 M HCl after reaction

Atmosphereflame-dried, Ar-purged flask; stirred under Ar

Temperature145

Timeovernight

Substrate orientationnot applicable

Oxidant / reductantnone reported

Work-upCool to RT; add 5 mL 1 M HCl; add to ice-cold H2O; collect by centrifugation; wash with EtOH, H2O, Et2O.

Activationdried under vacuum

Scalability context0.804 g dianhydride scale; product yield 1.367 g (84%).

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,4,5,8-Naphthalenetetracarboxylic dianhydride	0.804 g, 3.0 mmol	2 · General Materials and Experimental Methods
Linker	4-amino-3-hydroxy benzoic acid	1.01 g, 6.6 mmol	2 · General Materials and Experimental Methods
Solvent	anhydrous DMF	20 mL	2 · General Materials and Experimental Methods
Acid	HCl	5 mL · 1 M	2 · General Materials and Experimental Methods
Solvent	ice cold H2O	250 mL	2 · General Materials and Experimental Methods

Partial recipeSource: SI

Route 2: Solvothermal

12 · Three-dimensional electron diffraction measurements · Figure S8

Metal precursorsnot specified in this paper; likely Zr precursor by analogy to thin film route

Linker precursorsdcphOH-NDI

Solventsethanol used for dispersing prepared crystals before drop-casting; solvothermal synthesis solvent not specified for bulk crystals

Additivesnot specified

Atmospherenot specified

Substrate orientationdrop-cast onto copper grid covered in holey carbon film after synthesis for TEM/3DED

Oxidant / reductantnone reported

Work-upDispersed in ethanol, gently mortared, drop-cast onto holey-carbon copper grid; cooled in cryo-transfer holder before TEM.

Activationnot specified

Scalability contextOnly sample-preparation details for 3DED crystals are given; bulk solvothermal recipe is not detailed.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	dcphOH-NDI	not reported for bulk crystals	12 · Three-dimensional electron diffraction measurements · Figure S8
Solvent	ethanol	not reported · used for dispersing bulk crystals	12 · Three-dimensional electron diffraction measurements · Figure S8
Other	copper grid with holey carbon film	not reported	12 · Three-dimensional electron diffraction measurements · Figure S8

Complete recipeSource: Both

Route 3: Solvothermal

2-3 · Zr(dcphOH-NDI)@FTO thin film preparation

Metal precursorsZrCl4

Linker precursorsdcphOH-NDI linker

SolventsDMF; FTO cleaned in 1% Alconox/H2O, absolute EtOH and acetone; DMF rinsing/soaking

Additivesglacial acetic acid modulator; dcphOH-NDI SAM on FTO

AtmosphereFTO dried under N2 stream; synthesis vial atmosphere not otherwise specified

Temperature120

Time72

Substrate orientationSAM-modified FTO propped against vial wall, tilted, Teflon-side at vial bottom and FTO side facing up toward bulk solution; about 1 cm2 exposed

Oxidant / reductantnone reported

Work-upRemove substrate, unwrap Teflon tape, rinse with fresh DMF, soak in DMF until analysis.

ActivationNo evacuation before voltammetry; films kept solvent-swelled and dried under N2 only immediately before electrochemical cell introduction.

Scalability contextFTO pieces about 1 x 2 cm with about 1 cm2 exposed area; 20 mL vial synthesis solution.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	23.3 mg, 0.10 mmol	2-3 · Zr(dcphOH-NDI)@FTO thin film preparation
Linker	dcphOH-NDI	53.8 mg, 0.10 mmol · 1 mM SAM solution before MOF growth; 0.10 mmol in synthesis solution	2-3 · Zr(dcphOH-NDI)@FTO thin film preparation
Acid	glacial acetic acid	286 uL, 5 mmol	2-3 · Zr(dcphOH-NDI)@FTO thin film preparation
Solvent	DMF	8 mL synthesis solution plus rinsing/soaking · anhydrous for SAM solution	2-3 · Zr(dcphOH-NDI)@FTO thin film preparation
Other	fluorine-doped tin oxide (FTO)	~1 x 2 cm pieces, ~1 cm2 exposed	2-3 · Zr(dcphOH-NDI)@FTO thin film preparation