Issue 15, 2021

Scrutinizing ligand exchange reactions in the formation of the precious group metal–organic framework RuII,II-HKUST-1: the impact of diruthenium tetracarboxylate precursor and modulator choice

Abstract

The precious group metal (PGM) analogues of the iconic metal–organic framework [Cu3(BTC)2] (HKUST-1; BTC = 1,3,5 benzenetricarboxylate) still represent a synthetic challenge, especially if targeting the univalent and ideally defect-free RuII,II variant. Herein we present a systematic study employing the controlled secondary building unit approach (CSA) by using a variety of diruthenium tetracarboxylate complexes [Ru2(RCO2)4] as precursors in the synthesis of univalent Ru-HKUST-1 samples. Carboxylate ligand exchange test reactions suggest the importance of a pKa match between precursor ligand and BTC linker. For example, L-mandelate substituted precursors resulted in the most “perfect” samples of the investigated series with a fourfold increase in crystalline domain sizes compared to the established acetate route (according to PXRD and HR-TEM), high compositional purity (FT-IR, Raman, TGA and elemental analysis) and feature a so far unprecedentedly high BET surface area of 1789 m2 g−1 with the expected pore size distribution and total pore volume all similar to the ideal HKUST-1 parent structure.

Graphical abstract: Scrutinizing ligand exchange reactions in the formation of the precious group metal–organic framework RuII,II-HKUST-1: the impact of diruthenium tetracarboxylate precursor and modulator choice

Supplementary files

Article information

Article type
Paper
Submitted
13 Jan 2021
Accepted
15 Mar 2021
First published
15 Mar 2021

Dalton Trans., 2021,50, 5226-5235

Scrutinizing ligand exchange reactions in the formation of the precious group metal–organic framework RuII,II-HKUST-1: the impact of diruthenium tetracarboxylate precursor and modulator choice

W. R. Heinz, D. Staude, D. Mayer, H. Bunzen and R. A. Fischer, Dalton Trans., 2021, 50, 5226 DOI: 10.1039/D1DT00118C

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