Synthesis · A Nanotubular Metal–Organic Framework with a Narrow Bandgap from Extended Conjugation**

2 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 of Copper 5,10,15,20-Tetrakis [p-phenylphosphonic acid] porphyrin

Metal precursorsCuCl2 (360 mg, 2.67 mmol)

Linker precursorsFree-base porphyrin derivative H8-TPPA (500 mg, 0.53 mmol)

SolventsCHCl3 (50 mL); CuCl2 solution in 30 mL DMSO/MeOH (2/1)

Atmosphereargon

Temperature60

Time24

Work-upSolvent evaporated under vacuum; red solid washed with ethyl alcohol, ethyl acetate and acetone in order.

Scalability contextReported on 500 mg H8-TPPA scale, giving 425 mg product in 80% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H8-TPPA	500 mg, 0.53 mmol	2 · Synthesis of Copper 5,10,15,20-Tetrakis [p-phenylphosphonic acid] porphyrin
Metal Source	CuCl2	360 mg, 2.67 mmol	2 · Synthesis of Copper 5,10,15,20-Tetrakis [p-phenylphosphonic acid] porphyrin
Solvent	CHCl3	50 mL	2 · Synthesis of Copper 5,10,15,20-Tetrakis [p-phenylphosphonic acid] porphyrin
Solvent	DMSO/MeOH (2/1)	30 mL	2 · Synthesis of Copper 5,10,15,20-Tetrakis [p-phenylphosphonic acid] porphyrin

Complete recipeSource: Both

Route 2: Solvothermal

3 · Synthesis of GTUB-4

Metal precursorsCu-H8TPPA (10 mg, 0.01 mmol) as Cu-porphyrin linker; Ni(CH3COO)2.4H2O (7.5 mg, 0.03 mmol)

Linker precursorsCu-H8TPPA (10 mg, 0.01 mmol)

SolventsDMF/H2O (10 mL/7.5 mL)

Additivesphenylphosphonic acid (PPA) (238 mg, 1.5 mmol) modulator

Atmospheresealed glass scintillation vial; atmosphere not otherwise specified

Temperature80

Time72 (SI); 24 reported in main text

Work-upAfter sonication and heating, dark red needle-like crystals formed and were obtained with quantitative yield; isolation/washing details not further specified.

ActivationNo activation procedure reported.

Scalability contextSmall sealed-vial synthesis in a 20 mL glass scintillation vial; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Cu-H8TPPA	10 mg, 0.01 mmol	3 · Synthesis of GTUB-4
Additive	phenylphosphonic acid (PPA)	238 mg, 1.5 mmol	3 · Synthesis of GTUB-4
Metal Source	Ni(CH3COO)2.4H2O	7.5 mg, 0.03 mmol	3 · Synthesis of GTUB-4
Solvent	DMF/H2O	10 mL/7.5 mL	3 · Synthesis of GTUB-4