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The SALSAC Approach: Comparing the reactivity of solventdispersed nanoparticles with nanoparticulate surfaces

Freimann, Sven and Zare, Davood and Housecroft, Catherine E. and Constable, Edwin C.. (2020) The SALSAC Approach: Comparing the reactivity of solventdispersed nanoparticles with nanoparticulate surfaces. Nanoscale Advances, 2 (2). pp. 679-690.

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Official URL: https://edoc.unibas.ch/75683/

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Abstract

We demonstrate that the 'surface-as-ligand, surface-as-complex' (SALSAC) approach that we have established for annealed nanoparticulate TiO2 surfaces can be successfully applied to nanoparticles (NPs) dispersed in solution. Commercial TiO2 NPs have been activated by initial treatment with aqueous HNO3 followed by dispersion in water and heating under microwave conditions. We have functionalized the activated NPs with anchoring ligands 1-4; 1-3 contain one or two phosphonic acid anchoring groups and 4 has two carboxylic acid anchors; ligands 1, 2 and 4 contain 6,6'-dimethyl-2,2'-bipyridine (Me2bpy) metal binding domains and 3 contains a 2,2':6',2"-terpyridine (tpy) unit. Ligand functionalization of the activated NPs has been validated using infrared and 1H NMR spectroscopies, and thermogravimetric analysis. NPs functionalized with 1, 2 and 4 react with [Cu(MeCN)4][PF6] and those with 3 react with FeCl2 .4H2O; metal binding has been investigated using solid-state absorption spectroscopy and scanning electron microscopy (SEM). Competitive binding of ligands 1-4 to TiO2 NPs has been investigated and shows preferential binding of phosphonic acid over carboxylic acid anchors. For the phosphonic acids, the binding orders are 3 > 1 > 2 which is rationalized in terms of relative pKa values (phosphonic acid and [HMe2bpy]+ or [Htpy]+) and the number of anchoring groups in the ligands. Ligand exchange between ligandfunctionalized NPs and homoleptic metal complexes gives NPs functionalized with heteroleptic copper(I) or iron(II) complexes
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Freimann, Sven and Zare, Davood
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
e-ISSN:2516-0230
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
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Last Modified:21 Feb 2020 13:43
Deposited On:21 Feb 2020 13:43

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