van der Waals Solids from Self-Assembled Nanoscale Building Blocks

Choi, Bonnie; Yu, Jaeeun; Paley, Daniel W.; Trinh, M. Tuan; Paley, Maria V.; Karch, Jessica M.; Crowther, Andrew C.; Lee, Chul‐Ho; Lalancette, Roger A.; Zhu, Xiaoyang; Kim, Philip; Steigerwald, Michael L.; Nuckolls, Colin; Roy, Xavier

doi:10.1021/acs.nanolett.5b05049

Cited by 63 publications

(60 citation statements)

References 28 publications

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“…On the contrary, far less widespread are thin‐layered materials derived from self‐assembled supramolecular systems, whose weak interlayer noncovalent chemical interactions are van der Waals in nature. Such molecule‐based 2D materials may provide significant benefits toward physical and chemical tunability, structural flexibility, and ease of exfoliation . There is recent intensifying interest in an emergent class of 2D nanosheets constructed by downsizing 3D metal–organic frameworks (MOFs),[3a,7] which are inorganic–organic (hybrid) structures possessing an enormous physicochemical and structural versatility .…”

Section: Methodsmentioning

confidence: 99%

Optochemically Responsive 2D Nanosheets of a 3D Metal–Organic Framework Material

et al. 2017

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chemical tunability, structural flexibility, and ease of exfoliation. [6] There is recent intensifying interest in an emergent class of 2D nanosheets constructed by downsizing 3D metal-organic frameworks (MOFs), [3a,7] which are inorganic-organic (hybrid) structures possessing an enormous physicochemical [8] and structural versatility. [9] Furthermore, the nanoscale porosity of MOFs could function as a vessel to "host" a variety of functional "guest" molecules, [10] imparting a unique combination of properties through intimate host-guest interactions. [11] Yet, preparation of a functionalized MOF as 2D nanosheets exemplifying a tunable host-guest sensing response is uncommon in literature, unlike its traditional counterparts. [12] In this work, we present a simple supramolecular self-assembly strategy to accomplish concomitant 2D nanosheet synthesis and functionalization of a porous MOF system, and demonstrate its efficacy for application as a tunable optochemical sensor. We leverage our recently elucidated supramolecular "high-concentration reactions" (HCR) approach, [13] to realize one-pot synthesis of functionalized MOF nanosheets at ambient conditions; the basic concept is illustrated in Scheme 1. Here we describe a representative study employing 1,4-benzenedicarboxylic acid (BDC) as the organic linker, because of its strong propensity to construct an extended chemical network upon coordination with metal centers; for instance, here we utilized divalent Zn 2+ . Triethylamine base (NEt 3 ) featuring a flexible tripodal geometry was used to trigger fast activation (deprotonation) of the BDC linkers. [14] It is striking to see that, a white gel-like fibrous soft matter was immediately obtained at room temperature (Figure 1a), arising from the HCR between Zn 2+ and BDC 2− , augmented by the NEt 3 + cations. We observed a discernible twostage material transformation via optical microscopy ( Figure 1b): initially witnessing development of highly oriented fibers, prior to formation of a visually shiny phase prevalent on the fiber surfaces. The gel fiber diameter was found to be ≈1-10s µm by scanning electron microscopy (SEM), see Figure 1c. Intriguingly, SEM revealed those supramolecular fibers are, in fact, constituting densely packed crystalline nanosheets (Figure 1d), thus confirming the (shiny) faceted appearance detected under optical microscopy ( Figure 1b). To establish the detailed 2D morphologies, we examined nanosheets harvested from the supramolecular gels using transmission electron micro scopy (TEM) and SEM (Figure 1e,f), as well as by atomic force microscopy (AFM) with which we have estimated the nominal thickness of 2D nanosheets are contemporary materials with exceptional physical and functional properties, derived from a broad class of low-dimensional solids containing atomically thin structures, [1] exfoliated 2D frameworks, [2] and molecular membranes.[3] Considerable efforts are being devoted to 2D graphene-related materials [4] to yield improved mechanical, electronic, and optical modulat...

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Section: Methodsmentioning

confidence: 99%

Optochemically Responsive 2D Nanosheets of a 3D Metal–Organic Framework Material

et al. 2017

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“…Building on this foundation, our team has been developing a new class of solid state materials assembled from electronically and structurally complementary molecular clusters. These materials, which we term superatomic crystals, provide a bridge between traditional semiconductors, molecular solids, and nanocrystal arrays by combining tunability and atomic precision. Fullerenes have been particularly useful to produce collective properties in superatomic crystals, including ferromagnetic ordering, coherent thermal transport and semiconducting behavior …”

Section: Figurementioning

confidence: 99%

Dimerization of Endohedral Fullerene in a Superatomic Crystal

Voevodin

Abella

Castro

et al. 2017

Chemistry A European J

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We describe a solid state material created from the reaction of Ni9Te6(PEt3)8 and Lu3N@C80. The resulting superatomic crystal, [Ni12Te12(PEt3)8]2[(Lu3N@C80)2], contains dimers of Lu3N@C80 that form upon reduction of the fullerene through a single C−C bond at the triple hexagon junctions. The encapsulated Lu3N cluster displays an unprecedented orientation that is collinear and coplanar with the intercage carbon bond. Density functional theory calculations rationalize this unique bonding and relative orientation of the Lu3N clusters. Our structural and theoretical results provide new insights into the effect that the M3N cluster species has on the dimerization process of endohedral fullerenes.

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“…[32] Similar distances are obtained from high-resolution TEM and fast Fourier transform (FFT) (Supporting Information, Figure S4). SAED patterns from different samples consistently index to arhombohedral lattice with alattice parameter ranging from 16.4 to 17.2 .This corresponds to acentroid-to-centroid C 60 -C 60 distance of 9.47-9.93 ,which is slightly shorter than the corresponding distance of 9.65-9.94 measured by SCXRD in the pristine [Co 6 Se 8 (PEt 2 phen) 6 ][C 60 ] 5 .…”

Section: Angewandte Chemiementioning

confidence: 57%

Two‐Dimensional Fullerene Assembly from an Exfoliated van der Waals Template

et al. 2018

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Two-dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom-up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C as a polymerizable monomer. The C building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C . The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid.

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van der Waals Solids from Self-Assembled Nanoscale Building Blocks

Cited by 63 publications

References 28 publications

Optochemically Responsive 2D Nanosheets of a 3D Metal–Organic Framework Material

Optochemically Responsive 2D Nanosheets of a 3D Metal–Organic Framework Material

Dimerization of Endohedral Fullerene in a Superatomic Crystal

Two‐Dimensional Fullerene Assembly from an Exfoliated van der Waals Template

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