Synthesis · Efficient sequestration of radioactive 99TcO4- by a rare 3-fold interlocking cationic metal-organic framework: A combined batch experiments, pair distribution function, and crystallographic investigation

4 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. Synthesis · Scheme S1

Linker precursorsTPEPE ligand prepared through compound a and compound b from tetrakis(4-bromophenyl)ethene, trimethylsilylacetylene, and 4-iodopyridine

SolventsTriethylamine; dichloromethane; MeOH/NaOH; Et3N/THF (1/2); THF; CH2Cl2; petroleum ether; saturated NaCl solution

AdditivesCuI and PdCl2(PPh3)2 catalysts; NaOH deprotection

AtmosphereNitrogen for Sonogashira coupling steps; degassed before trimethylsilylacetylene addition

Temperature60; 65; room temperature

Time12; overnight; 0.2

Work-upCompound a extracted with dichloromethane and purified by column chromatography (CH2Cl2/petroleum ether = 1:20). Compound b washed with brine, evaporated and purified by chromatography (CH2Cl2/petroleum ether = 1:10). TPEPE reaction filtered, solvent removed, crude product dissolved in CH2Cl2, washed with saturated NaCl solution and purified by column chromatography.

Scalability contextGram-scale ligand precursor quantities are reported in the SI; no explicit scale-up discussion.

Show 9 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	tetrakis(4-bromophenyl)ethene	1.20 g, 1.85 mmol	2. Synthesis · Scheme S1
Additive	CuI	8.76 mg, 0.05 mmol; 327 mg, 3% mol	2. Synthesis · Scheme S1
Additive	PdCl2(PPh3)2	64.7 mg, 0.09 mmol; 1.20 g, 3% mol	2. Synthesis · Scheme S1
Other	trimethylsilylacetylene	1.70 g, 17 mmol	2. Synthesis · Scheme S1
Solvent	triethylamine	20 mL	2. Synthesis · Scheme S1
Base	NaOH in MeOH	0.54 g NaOH / 30 mL MeOH	2. Synthesis · Scheme S1
Other	4-iodopyridine	11.8 g, 57.6 mmol	2. Synthesis · Scheme S1
Other	Compound b (tetrakis(4-ethynylphenyl)ethane)	4.92 g, 11.5 mmol	2. Synthesis · Scheme S1
Solvent	Et3N/THF (1/2)	80 mL plus 60 mL THF for compound b solution	2. Synthesis · Scheme S1

Complete recipeSource: Both

Route 2: Solvothermal

2. Synthesis

Metal precursorsNi(NO3)2.xH2O, 30 mg, 0.1 mmol

Linker precursorstetrakis(4-(4-(pyridyl)ethynyl)phenyl)ethene (TPEPE), 10 mg, 0.014 mmol

SolventsCH3CN/DMSO, 12 mL, v/v 10/2

AtmosphereNot specified; dried in air after synthesis

Temperature120

Time48

Work-upCooled to room temperature; product washed with H2O and EtOH; yellow crystals dried in air at room temperature.

ActivationNo separate activation reported in the main text.

Scalability contextBatch in 20 mL Teflon-lined steel autoclave; no scale-up information reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	tetrakis(4-(4-(pyridyl)ethynyl)phenyl)ethene	10 mg, 0.014 mmol	2. Synthesis
Metal Source	Ni(NO3)2.xH2O	30 mg, 0.1 mmol	2. Synthesis
Solvent	CH3CN/DMSO	12 mL, v/v 10/2	2. Synthesis
Solvent	H2O wash	Not specified	2. Synthesis
Solvent	EtOH wash	Not specified	2. Synthesis

Partial recipeSource: Main

Route 3: Other

2 · 2.1. Synthesis of ZJU-X6

Metal precursorsPre-formed ZJU-X6

SolventsAqueous ReO4- solution

AtmosphereNot specified

Time12

Work-upExpose a small amount of ZJU-X6 in 2 mL of 1000 ppm ReO4- solution for 12 h.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	ZJU-X6	small amount	2 · 2.1. Synthesis of ZJU-X6
Additive	ReO4- solution	2 mL · 1000 ppm	2 · 2.1. Synthesis of ZJU-X6

Partial recipeSource: Main

Route 4: Other

2 · 2.1. Synthesis of ZJU-X6

Metal precursorsPre-formed ZJU-X6

SolventsAqueous 99TcO4- solution

AtmosphereNot specified

Time12

Work-upExpose a small amount of ZJU-X6 in 2 mL of 1000 ppm 99TcO4- solution for 12 h.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	ZJU-X6	small amount	2 · 2.1. Synthesis of ZJU-X6
Additive	99TcO4- solution	2 mL · 1000 ppm	2 · 2.1. Synthesis of ZJU-X6