Titanium-Oxide Host Clusters with Exchangeable Guests

Zhang, Guanyun; Li, Wenyun; Liu, Caiyun; Jia, Jiong; Tung, Chen‐Ho; Wang, Yifeng

doi:10.1021/jacs.7b10565

Cited by 82 publications

(58 citation statements)

References 39 publications

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“…Since the discovery of crown ethers, cryptands, and spherands in the 1960s by the groups of Pedersen, Lehn, and Cram, respectively, supramolecular chemistry has gradually become a branch of paramount importance of modern chemistry [10] . The term “host–guest chemistry” [11] was introduced as early as 1974 to describe the chemistry of cyclic or cage hosts with smaller guests.…”

Section: Host–guest Clustersmentioning

confidence: 99%

“…Recently, we reported new titanium oxide hosts, {Ti 12 O 18 } (in this context, {Ti x O y } is used to designate the TOCs exhibiting the same Ti x O y core, whereas Ti number is the abbreviation of a specific TOC), which selectively encloses univalent cations, according to the size‐complementarity law [10] . It features a unique hexagonal prismatic Ti 12 O 18 12+ framework (Figure 1 a and b).…”

Section: Host–guest Clustersmentioning

confidence: 99%

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Supramolecular Chemistry of Titanium Oxide Clusters

Liu

Wang

2021

Chemistry A European J

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Titanium oxide clusters (TOCs) have been emerging as a new type of inorganic molecular entities of supramolecular chemistry. Herein, a perspective on the structures and functionalities of TOCs over the past three decades is given and the paramount roles of TOCs in serving supramolecular chemistry are demonstrated. Four types of supramolecular assemblies based on TOCs are reviewed, namely, TOC hosts for ion inclusion, mechanically interlocked molecular systems built from cyclic TOCs, reactivities of surface sites toward ligand exchange, and hierarchical structures of TOCs. The principles and advantages of TOCs toward each application are fully discussed, along with structural analyses. Following this path, more functional TOC‐based supramolecular systems may be designed and synthesized in the future, which, in turn, will certainly enhance research into both supramolecular and coordination chemistry of titanium.

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Section: Host–guest Clustersmentioning

confidence: 99%

Section: Host–guest Clustersmentioning

confidence: 99%

Supramolecular Chemistry of Titanium Oxide Clusters

Liu

Wang

2021

Chemistry A European J

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“…Ti–oxo clusters are widely considered as a TiO 2 nanomaterial at a molecular level, and receive considerable attention due to their structural diversity as well as potential applications in catalysis, biomedicine and environments. [ 48 ] The number of Ti atoms in Ti–oxo clusters ranges from 3 to 32, including Ti 3 , [ 49–52 ] Ti 4 , [ 50,52–57 ] Ti 5 , [ 57 ] Ti 6 , [ 51,52,54,55,57–64 ] Ti 7 , [ 57 ] Ti 8 , [ 54,64,65 ] Ti 9 , [ 51,55,63 ] Ti 10 , [ 66 ] Ti 11 , [ 54–56,63 ] Ti 12 , [ 57,62,66,67 ] Ti 14 , [ 50,56 ] Ti 16 , [ 54,55,61,66 ] Ti 18 , [ 51,57 ] Ti 19 , [ 63 ] Ti 20 , [ 66,68 ] and Ti 32 clusters. [ 69 ] In general, during the assembly of Ti–oxo clusters, it is vital to control the competition between acids and coordinating ligands.…”

Section: Cluster Chemistry Of Group 3 and 4 Metalsmentioning

confidence: 99%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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“…[1] For instance, titanium-oxo clusters (TOCs) are widely regarded as model molecules of the well-known titanium oxide (TiO 2 ) nanomaterials, [2] and tremendous progress has been made on the TOCs in that their atomically precise structures could offer the opportunity to investigate structures and reactivities of TiO 2 at a molecular level. [2,3] Compared with TiO 2 only absorbing UV light, silver orthophosphate (Ag 3 PO 4 ) semiconducting material has recently received extensive attention as a newly developed photocatalyst, which exhibits excellent catalytic activities for dye degradation and water oxidation to O 2 under visible-light irradiation. [4,5] Associating TOCs intimately with TiO 2 , silver orthophosphate clusters (SOCs) could be considered as important molecular analogues of bulk nanoscale Ag 3 PO 4 , which may provide useful insights in comprehending the electronic structures and binding modes of pure Ag 3 PO 4 on the molecular scale.…”

Section: Thechemistryofclusterscontinuallyattractinterdisciplinarymentioning

confidence: 99%

A Sodalite‐Type Silver Orthophosphate Cluster in a Globular Silver Nanocluster

et al. 2020

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The synthesis and structure of a giant 102‐silver‐atom nanocluster (NC) 1 is presented. X‐ray structural analysis reveals that 1 features a multi‐shelled metallic core of Ag6@Ag24@Ag60@Ag12. An octahedral Ag6 core is encaged by a truncated octahedral Ag24 shell. The Ag24 shell is composed of a hitherto unknown sodalite‐type silver orthophosphate cluster (SOC) {(Ag3PO4)8}, reminiscent of the Ag3PO4 photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag6@{(Ag3PO4)8}S6]6−, which functions as an intricate polyhedral template with abundant surface O and S atoms guiding the formation of a rare rhombicosidodecahedral Ag60 shell. An array of 6 linear Ag2 staples further surround this Ag60 shell. [Ag6@{(Ag3PO4)8}S6]6− is an unusual Ag‐based templating anion to induce the assembly of a SOC within silver NC. This finding provides molecular models for bulk Ag3PO4, and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.

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Titanium-Oxide Host Clusters with Exchangeable Guests

Cited by 82 publications

References 39 publications

Supramolecular Chemistry of Titanium Oxide Clusters

Supramolecular Chemistry of Titanium Oxide Clusters

Metal–Organic Frameworks Based on Group 3 and 4 Metals

A Sodalite‐Type Silver Orthophosphate Cluster in a Globular Silver Nanocluster

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