Built to Order:  Molecular Tinkertoys from the [Re6(μ3-Se)8]2+ Clusters

Roland, Bryan K.; Selby, Hugh D.; Carducci, Michael D.; Zheng, Zhiping

doi:10.1021/ja025869r

Cited by 78 publications

(35 citation statements)

References 16 publications

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“…The dominate, common synthetic approach to such solids is through metal salt coordination to reactive groups on the capping ligands of the superatoms (for examples, see DiSalvo, Long, Fedorov, and Zheng). Superatoms with rhenium are particularly prominent in these examples, as their chemistry has been richly developed: site‐differentiated [Re 6 Se 8 ] superatoms have been synthesized and extensively studied, as well as their assembly into oligomers, supramolecular arrays, and dendrimers . These assemblies, while structurally interesting, do not exhibit significant inter‐superatom interactions.…”

Section: Materials From Superatomsmentioning

confidence: 99%

Dimensional Control of Assembling Metal Chalcogenide Clusters

et al. 2020

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The ability to synthesize novel functional materials at the nanoscale relies on the design and synthesis of versatile, tunable, atomically precise building blocks. Clusters of atoms exhibit physical properties beyond those of their constituent atoms, and new phenomena (e.g. electronic, magnetic) can emerge in such materials. This minireview describes a method to create site-differentiated clusters and presents various synthetic approaches toward creating materials from these building blocks. The cobalt selenide clusters fundamental to this study are members of a larger class of clusters with the [M 6 E 8 ] [a] rials and give rise to controlled reactions in 1-, 2-, and 3-dimensions (1D, 2D, and 3D). The focus of this minireview is on a toolbox of regiochemically pure, atomically precise [Co 6 Se 8 (CO) x (PEt 3 ) 6-x ] superatoms. The CO functionalization is a synthetically useful handle that can be easily manipulated to determine the dimensionality in the desired direction. Through these building blocks we have created linked oligomers, fused dimers by using carbene ligated superatoms, 2D woven polymers, and a 3D MOF with superatoms at the nodes (Figure 1). We will also detail the reaction chemistry that produces and then utilizes these new superatomic building blocks.Using the following methods we can control and tune the dimensionality and topology of our nanoscale building blocks:(1) solution-phase synthesis that allows us to synthesize COsubstituted superatoms and substitute them with other linkers and ligands, (2) electrocrystallization, a technique that allows for the assembly of a large variety of ions into single crystals of

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Section: Materials From Superatomsmentioning

confidence: 99%

Dimensional Control of Assembling Metal Chalcogenide Clusters

et al. 2020

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“…The facility of encapsulating biologically relevant clusters into dendrimers has further been illustrated by Aida et al [31], who prepared dendrimer encapsulated copper(µ-oxo)dimers (found in methane monooxygenase and ribonucleotide reductase) and Basu et al who prepared dendrimer encapsulated oxo-Mo(V)tetrasulfide units (found in DMSO reductase) [32]. Significant contributions have also come from Kaifer et al [33][34][35][36][37][38] who have reported dendrimers based on ferrocenyl and viologen core moieties and Zheng et al, who have reported dendrimers based on a Re 6 Se 8 cluster core moiety [39][40][41].…”

Section: Synthesis Of Metal Cluster Core Dendrimersmentioning

confidence: 99%

Dendritic encapsulation as probed in redox active core dendrimers

Gorman¹

2003

Comptes Rendus. Chimie

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“…Structural transformationst riggered by solvent, including for SCAMs, are interesting and useful, [8a,b] which could produce novel structures and have potential applications in molecular switches, sensors, data storage, and display devices. [7c, 9] Relativelys ubtle electronic modifications to the linker can induced iffering structures, [10] although there are as yet no reportede xamples of their influences in single-crystal to single-crystals tructural transformations. In addition,t he geometrical structure and electronic properties of the SCC are easily affected and transformed in solvents.…”

Section: Introductionmentioning

confidence: 99%

Linker Flexibility‐Dependent Cluster Transformations and Cluster‐Controlled Luminescence in Isostructural Silver Cluster‐Assembled Materials (SCAMs)

Wang

Huang

Wang

et al. 2019

Chemistry A European J

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Silver chalcogenolate clusters (SCCs) and silver cluster-assembled materials (SCAMs) are an importantc ategory of novel luminescentm aterials, the emission of which can be modulated by variationo ft he cluster nodes and linker species. Here, the successfully synthesis of two isostructural 2D SCAMs is reported: Ag 12 bpa and Ag 12 bpe are formed by using two linkers with different conformational freedom( bpa = 1,2-bis(4-pyridyl)ethane, bpe = 1,2-bis(4-pyridyl)ethylene), with dodenuclear silver chalcogenolatec lusters as secondary buildingu nits (SBUs). Interestingly,n onluminescent Ag 12 bpa at room temperature could quickly transform into 1D Ag 10 bpa,w ith concomitantd issociation of two silver atoms and the remaining ten silver atomsr earrangingi nt he cluster, thus exhibiting an intensey ellow phosphorescence after being triggeredb ya cetonitrile (CH 3 CN). Similarly,s timulating Ag 12 bpe with CH 3 CN, by contrast, gave another 2D structure Ag 12 bpe-1b with the dis-tortedS BUs and different topology structure, and both of them are merely red-emissivea tl ow temperature. To note, after exchanging ligands, room-temperature nonluminescent 2D Ag 12 bpe-1b can be transformed into intensely luminescent 1D Ag 10 bpa.T his linker-flexibility-dependent structural transformationa nd cluster-basedS BU controlled luminescence remainss carce.O ur work provides new insights into structure-luminescencer elationship in clustered metal-organic frameworks and intelligent stimulus-responsive luminescent materials.

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Built to Order: Molecular Tinkertoys from the [Re₆(μ₃-Se)₈]²⁺ Clusters

Cited by 78 publications

References 16 publications

Dimensional Control of Assembling Metal Chalcogenide Clusters

Dimensional Control of Assembling Metal Chalcogenide Clusters

Dendritic encapsulation as probed in redox active core dendrimers

Linker Flexibility‐Dependent Cluster Transformations and Cluster‐Controlled Luminescence in Isostructural Silver Cluster‐Assembled Materials (SCAMs)

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