Noncovalent Grafting of Molecular Complexes to Solid Supports by Counterion Confinement.

Autor: Laan PCM; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands., Bobylev EO; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands., Geels NJ; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands., Rothenberg G; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands., Reek JNH; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands., Yan N; Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands.; Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education, School of Physics and Technology, Wuhan University, Wuhan 430072, China.
Jazyk: angličtina
Zdroj: The journal of physical chemistry. C, Nanomaterials and interfaces [J Phys Chem C Nanomater Interfaces] 2023 Dec 12; Vol. 127 (50), pp. 24129-24136. Date of Electronic Publication: 2023 Dec 12 (Print Publication: 2023).
DOI: 10.1021/acs.jpcc.3c05691
Abstrakt: Grafting molecular complexes on solid supports is a facile strategy to synthesize advanced materials. Here, we present a general and simple method for noncovalent grafting on charge-neutral surfaces. Our method is based on the generic principle of counterion confinement in surface micropores. We demonstrate the power of this approach using a set of three platinum complexes: Pt 1 (Pt 1 L 4 (BF 4 ) 2 , L = p -picoline), Pt 2 (Pt 2 L 4 (BF 4 ) 4 , L = 2,6-bis(pyridine-3-ylethynyl)pyridine), and Pt 12 (Pt 12 L 24 (BF 4 ) 24 , L = 4,4'-(5-methoxy-1,3-phenylene)dipyridine). These complexes share the same counterion (BF 4 - ) but differ vastly in their size, charge, and structure. Imaging of the grafted materials by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and energy-dispersive X-ray (EDX) showed that our method results in a homogeneous distribution of both complexes and counterions. Nitrogen sorption studies indicated a decrease in the available surface area and micropore volume, providing evidence for counterion confinement in the surface micropores. Following the adsorption of the complexes over time showed that this is a two-step process: fast surface adsorption by van der Waals forces was followed by migration over the surface and surface binding by counterion confinement. Regarding the binding of the complexes to the support, we found that the surface-adsorbate binding constant ( K S ) increases quadratically with the number of anions per complex up to K S = 1.6 × 10 6 M -1 equaling Δ G ° ads = -35 kJ mol -1 for the surface binding of Pt 12 . Overall, our method has two important advantages: first, it is general, as you can anchor different complexes (with different charges, counterions, and/or sizes); second, it promotes the distribution of the complexes on the support surface, creating well-distributed sites that can be used in various applications across several areas of chemistry.
Competing Interests: The authors declare no competing financial interest.
(© 2023 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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