Colloidal Molecules from Valence‐Endowed Nanoparticles by Covalent Chemistry

Abstract

We demonstrate asimple method to create avariety of silica-based colloidal molecules through the covalent assembly of site-specifically functionalizedp atchy nanoparticles with complementary nanospheres.Colloidal analogues of BeBr 2 ,BBr 3 and CBr 4 are obtained from sp-, sp 2 -and sp 3 -like particles,while Br 2 Oand NBr 3 analogues can be fabricated by varying the relative amounts of both colloidal precursors.W e also show that it is possible to attach covalently silica nanospheres of various sizes to one central patchy nanoparticle, which leads to the formation of more complex colloidal molecules,i ncluding chiral ones.T he possibility to easily extend the strategy to other colloidal precursors whichc an serve as satellites,for example,ellipsoidal polymer particles or metallic nanoparticles,o pens the way to ar ich variety of new colloidal analogues of atoms whichc ould serve as building blocks of next generation materials.

Synthesis of ABn-type colloidal molecules by polymerization-induced particle-assembly (PIPA)

“…Colloidal molecules (CMs) are well-dened colloidal clusters with precise symmetry of molecular structures and have drawn extensive interest because of their unique properties 1,2 and potential as building blocks for low-coordination open structures. 3,4 With compartmental functional domains and directional interaction, CMs are promising in biological and medical applications, 5,6 self-assembly, 7,8 physical chemistry, [9][10][11] and materials science and technology. [12][13][14] Through particle-based self-assembly, CMs with molecule-like symmetries are enabled using monodisperse patchy building blocks with a suitable shape or interaction anisotropy.…”

Synthesis of Colloidal Molecules: Recent Advances and Perspectives

“…b) Scheme, cryoEM images and 3D structural model reconstructed from the cryoEM images of methane‐like CMs obtained by using a tetrahedral DNA cage . c) TEM images of AX 3 Y‐, AX 2 Y 2 , AXY 3 ‐ and AWXYZ‐like CMs (scale bars: 100 nm) . d) False‐colour SEM images of AX 4 ‐like CMs assembled via liquid bonds .…”

“…[52] c) TEM images of AX 3 Y-,A X 2 Y 2 ,AXY 3 -and AWXYZ-like CMs (scaleb ars:1 00 nm). [67] d) False-colour SEM images of AX 4 -like CMs assembled via liquid bonds. [69] e) SEM and confocal fluorescent images of patchy particles used as CAs (scale bars:5 00 nm) and bright-field, confocalf luorescenta nd schematic images of CMsa ssembled from them (scale bars:2mm).…”

“…[73] Adapted with permission from Refs. [49], [52], [ 67], [69], [ 70] and [73],copyright RSC 2017, ACS 2015,Wiley-VCH2 018,N PG 2017, NPG 2012and NAS 2018. staple strands, also called DNA origami, which allows one to design nanoscale DNA architectures with extensive shape control, has also been used to template the organizationo fD NA coated particles. One can place ag old nanoparticle in the center of an origami to create square-shaped or cross-shaped CMs.…”

“…cavities) that display well-defined symmetries can assemble with multiple complementary spherical particlesv ia depletion interaction [65] or spherical droplets via preferential wetting, [66] forming CMs with well-definedg eometries.W ed eveloped as imilars trategy in promoting the covalenta ttachment of complementary nanospheresw ith silica nanoparticles with 2, 3o r4dimples through the selective functionalization of PS residues remaining at the bottom of the dimples. [67,68] By varying the relative amountso fb oth precursors, the size or the chemicalc omposition of the complementary nanospheres, we createdal arge variety of CMs, including chiral ones (Figure 3c). An alternative approachisb ased on the use of particles with enthalpic patches, that is, zonesa tt heir surface which exhibit specific interactions, as precursors.…”