Complex supramolecular fiber formed by coordination-induced self-assembly of benzene-1,3,5-tricarboxamide (BTA)

Bohang Wu; Lin Liu; Lu Zhou; Jose Rodrigo Magana; Marco M R M Hendrix; Jiahua Wang; Chendan Li; Peng Ding; Yiming Wang; Xuhong Guo; Ilja K Voets; Martien A Cohen Stuart; Junyou Wang

doi:10.1016/j.jcis.2021.10.124

Complex supramolecular fiber formed by coordination-induced self-assembly of benzene-1,3,5-tricarboxamide (BTA)

J Colloid Interface Sci. 2022 Feb 15;608(Pt 2):1297-1307. doi: 10.1016/j.jcis.2021.10.124. Epub 2021 Oct 26.

Authors

Bohang Wu¹, Lin Liu¹, Lu Zhou², Jose Rodrigo Magana³, Marco M R M Hendrix⁴, Jiahua Wang¹, Chendan Li¹, Peng Ding⁵, Yiming Wang⁶, Xuhong Guo⁷, Ilja K Voets⁸, Martien A Cohen Stuart⁹, Junyou Wang¹⁰

Affiliations

¹ Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, 200237 Shanghai, China.
² Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, 200237 Shanghai, China. Electronic address: y30191016@mail.ecust.edu.cn.
³ Self-Organizing Soft Matter Lab, Department of Chemical Engineering and Chemistry & Institute for Complex Molecular Systems, Eindhoven University of Technology, 5612 AZ, the Netherlands. Electronic address: j.r.magana.rodriguez@tue.nl.
⁴ Self-Organizing Soft Matter Lab, Department of Chemical Engineering and Chemistry & Institute for Complex Molecular Systems, Eindhoven University of Technology, 5612 AZ, the Netherlands. Electronic address: m.m.r.m.hendrix@tue.nl.
⁵ Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, 200237 Shanghai, China. Electronic address: dingpeng@ecust.edu.cn.
⁶ Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, 200237 Shanghai, China. Electronic address: yimingwang@ecust.edu.cn.
⁷ Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, 200237 Shanghai, China. Electronic address: guoxuhong@ecust.edu.cn.
⁸ Self-Organizing Soft Matter Lab, Department of Chemical Engineering and Chemistry & Institute for Complex Molecular Systems, Eindhoven University of Technology, 5612 AZ, the Netherlands. Electronic address: i.voets@tue.nl.
⁹ Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, 200237 Shanghai, China. Electronic address: martien.cohenstuart@wur.nl.
¹⁰ Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, 200237 Shanghai, China. Electronic address: junyouwang@ecust.edu.cn.

PMID: 34739992
DOI: 10.1016/j.jcis.2021.10.124

Abstract

Hypothesis: In the quest for large but well-controlled supramolecular structures, the discotic benzene-1,3,5-tricarboxamide (BTA) has received quite some attention, because it can form hydrogen-bonded stacks that can be regarded as supramolecular polymers of which the single BTA molecule is the monomer. In this report, we consider a more complex BTA-based supramolecular polymer, namely one that is built up from supramolecular 'monomers'.

Experiments: We design a tris-ligand L₃ consisting of a BTA core carrying three dipicolinic acid (DPA) groups. L₃ itself is too small to form polymers, but in the presence of appropriate metal ions, each L₃ can form three coordination bonds and so form (L₃)_n clusters that are large enough to stack successfully: at an appropriate metal dose, long and stable filaments with a cross-sectional diameter of 12 nm appear. We monitor the growth process by UV-vis spectroscopy and light scattering, and use small angle X-ray scattering (SAXS), TEM as well as molecular simulation to confirm the filamentous structure of the fibers and determine their dimensions.

Findings: The formation and structure of the fiber are very similar for various transition metal ions, which enables introducing different functionalities, e.g., magnetic relaxivity, by proper choice of the metal ions. Hence, we obtain a doubly supramolecular polymer, connected axially by hydrogen bonds, and radially by coordination bonds. Not only does this realize a higher level of complexity, but it also allows to easily introduce and vary metal-derived functionalities.

Keywords: Benzene-1,3,5-tricarboxamide; Complex supramolecular fiber; Coordination; Self-assembly.

MeSH terms

Benzamides*
Benzene*
Scattering, Small Angle
X-Ray Diffraction

Substances

Benzamides
benzene-1,3,5-tricarboxamide
Benzene