All-catecholate-stabilized black titanium-oxo clusters for efficient photothermal conversion

Chemical Science, Год журнала: 2024, Номер 15(7), С. 2655 - 2664

Опубликована: Янв. 1, 2024

We synthesize a black titanium oxo cluster, Ti16, entirely surrounded by catechol ligands. This cluster exhibits an extremely low optical band gap and exceptional stability, endowing it with superior photothermal photoelectric capabilities.

Язык: Английский

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Polyoxometalates Embedded into Covalent Triazine Frameworks Regulating Charge Transfer for Visible-Light-Driven Synthesis of Functionalized Sulfoxides and Detoxification of Mustard Gas Simulants

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(4), С. 1655 - 1665

Опубликована: Янв. 17, 2024

For environmentally friendly and sustainable development demands, visible-light-driven oxidation of sulfides has become one the most popular strategies to synthesize functionalized sulfoxides degrade mustard gas simulants. Herein, three novel polyoxometalate-based covalent triazine frameworks, SiW12-CTF (1), PW12-CTF (2) PMo12-CTF (3) (CTF = framework), were synthesized via hydrothermal reaction characterized by infrared spectroscopy, powder X-ray diffraction, XPS spectroscopy UV–vis DRS, etc. These compounds are excellent photocatalysts for selective synthesis various as well degradation 2-chloroethyl ethyl sulfide (CEES) illuminated a 10 W 425 nm LED in an O2 atmosphere. Oxygen-rich POMs with strong electronegativity modulate electronic structure create built-in electric field POM-CTFs, which promotes separation migration photogenerated carriers. Meanwhile, encapsulation POM guests into CTF induces different electron transfer behaviors, resulting photocatalytic activities. Specifically, PW12-CTF, visible-light-induced methyl phenyl sulfide, obtain sulfoxide yields 96% 88% within 2 h, respectively, is higher than (68%) SiW12 (5%). However, exhibits inferior properties, yield 35% under same conditions. The in-depth mechanism reveals that process dominated O2•– energy induced 1O2 exist system. In addition, can be used catalyze sulfur-containing maintains boosted structural stability catalytic activity after reaction.

Язык: Английский

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Polyoxometalate‐Based Frameworks: Construction Strategies and Photocatalytic Applications

ChemCatChem, Год журнала: 2024, Номер 16(14)

Опубликована: Фев. 28, 2024

Abstract Polyoxometalate‐based frameworks, as a kind of material constructed by polyoxometalates (POMs), metal ions or clusters, organic ligands, are combined both the advantages oxygen‐rich POMs and porous metal‐organic frameworks (MOFs) within one single system. This integration greatly expands their potential applications compared to individual MOFs. Particularly for photocatalysis, narrow light absorption range typical units in ultraviolet region hinders extensive uses visible‐light‐driven photocatalysts. However, incorporation photoactive into POMs‐based can be considered an effective approach overcome this limitation. In paper, we review selected examples recent progress based on POM‐based along with construction strategies various areas mainly including water splitting, CO 2 reduction, synthesis also selective coupling reactions.

Язык: Английский

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Homoselective Synthesis of tetrazoles and chemoselective oxidation of sulfides using Ni(II)-Schiff base complex stabilized on 3-dimensional mesoporous KIT-6 surface as a recyclable nanocatalyst

Inorganic Chemistry Communications, Год журнала: 2023, Номер 160, С. 111852 - 111852

Опубликована: Дек. 11, 2023

Язык: Английский

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PW12-M@COFs as efficient photocatalysts for visible-light-driven oxidation of various sulfides and degradation of chemical warfare agent simulant

Applied Catalysis A General, Год журнала: 2023, Номер 662, С. 119283 - 119283

Опубликована: Май 27, 2023

Язык: Английский

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Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Journal of Catalysis, Год журнала: 2024, Номер 436, С. 115627 - 115627

Опубликована: Июль 1, 2024

Язык: Английский

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Inorganic Borate Functionalized {Ni₆SiW₉} Polyoxometalates: From Cluster to Cage Cluster

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

In aqueous solution systems, an all-inorganic Ni6-added polyoxometalate (Ni6AP) [Ni6(μ3-OH)3(H2O)12(B-α-SiW9O34)]1- ({Ni6SiW9}, here, {Ni6} = Ni6(μ3-OH)3(H2O)12) has been made via a hydrothermal method. By introducing inorganic boron sources, B3O3(OH)6 ({B3}) cluster was precisely anchored onto to form [B3O3(OH)6Ni6(μ3-OH)2(H2O)8(B-α-SiW9O34)]3- ({B3Ni6(OH)2(H2O)8SiW9}) through replacing four terminal water molecules and condensing with one hydroxyl of the cluster. Subsequently, addition further sources facilitated in situ growth B-O clusters on basis {B3Ni6(OH)2(H2O)8SiW9}, which resulted successful synthesis {[B7O8O2/3(OH)6Ni6(μ3-OH)2(H2O)8(B-α-SiW9O34)]3}7- ({B7Ni6(OH)2(H2O)8SiW9}3 or {B21}@{Ni6(OH)2(H2O)8SiW9}3). It is first cage constructed by NiAPs clusters, successfully realizes borate functionalized POMs from single The central {B7O8O2/3(OH)6}3 ({B21}) exhibits uncommon cavity configuration. Meanwhile, we have conducted discussion possible formation mechanism NiAPs. Furthermore, these three compounds efficiently accelerate oxidative transformation sulfides, number B atoms relatively affects selectivity products.

Язык: Английский

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Structural Diversity of Nucleotide Coordination Polymers of Cytidine Mono-, Di-, and Tri-Phosphates and Their Selective Recognition of Tryptophan and Tyrosine

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Understanding the coordination geometry of nucleotide mono-, di-, and triphosphates is pivotal for unraveling intricate relationships between molecular structure biological function, particularly in metal-ligand interactions their role biomolecular recognition. This study investigates nucleotide-metal polymers selective with amino acids, specifically tryptophan (Trp) tyrosine (Tyr). We synthesized comprehensively analyzed five cytidine nucleotides: monophosphate (CMP), deoxycytidine (dCMP), diphosphate (CDP), triphosphate (CTP), which are {[Cu(CMP)(bpa)(H2O)3](CMP)·3H2O}n (1), {[Cu2(dCMP)(4,4'-bipy)2(H2O)2]·4H2O}n (2), {[Cu2(CDP)2(azpy)(H2O)]·3H2O}n (3), {[Cd2(CDP)2(bpa)2(H2O)2]·8H2O}n (4), {[Cu(CTP)(2,2'-bipy)]·2H2O}n (5), where (4) (5) mark first report CDP CTP complexes. Single-crystal X-ray diffraction unveiled to be one-dimensional (1, 5) or two-dimensional (2, 3, 4). Circular dichroism (CD) spectroscopy both solid solution states elucidates chirality-driven assembly these polymers. The (Tyr) were studied using spectroscopic titrations. Experimental computational analyses reveal distinct all highlighting biosensing potential. Binding affinity variations across offer insights into chemistry suggest applications recognition functional materials.

Язык: Английский

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A Porous Carbazolic Al-MOF for Efficient Aerobic Photo-Oxidation of Sulfides into Sulfoxides under Air

Inorganic Chemistry, Год журнала: 2024, Номер 63(10), С. 4707 - 4715

Опубликована: Фев. 27, 2024

A robust, microporous, and photoactive aluminum-based metal–organic framework (Al-MOF, LCU-600) has been assembled by an in situ-formed [Al3O(CO2)6] trinuclear building unit a tritopic carbazole ligand. LCU-600 shows high water stability permanent porosity for N2 CO2 adsorption. Notably, the incorporation of photoresponsive moieties into makes it highly efficient recyclable photocatalyst aerobic photo-oxidation sulfides sulfoxides under air atmosphere at room temperature. Mechanism investigations unveil that photogenerated holes (h+), superoxide radical anion (O2•–), singlet oxygen (1O2) are critical active spices reaction performed atmosphere.

Язык: Английский

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Visible-Light-Responsive 2D Photocatalysts Assembled by Evans–Showell-Type POMs and Metalloviologen Frameworks for Sulfide–Sulfoxide Transformation

Inorganic Chemistry, Год журнала: 2023, Номер 62(26), С. 10120 - 10130

Опубликована: Июнь 22, 2023

Sulfide-sulfoxide aerobic photo-oxidation is of great interest in organic and medicinal chemistry; however, developing efficient facile heterogeneous photocatalytic systems without additional additives remains challenging. Herein, we intentionally designed synthesized two polyoxometalate (POM)-based metalloviologen frameworks, formulated as [MII(4-PBPY)2(H2O)][MII(H2O)4][CoIII2MoVI10H4O38]·nH2O (M = Cu, n 10 for 1; M Co, 11 2), prepared by the mild one-step synthesis strategy characterized detail. X-ray single-crystal diffraction analysis shows that they present a two-dimensional layered structure formed parallel layers pillared dimeric Evans-Showell-type POMs. The connection POM to framework enables easier flow electrons port, which can theoretically further induce O2 generate reactive oxygen species (O2•-) oxidize substrates form target products. As expected, both 1 2 exhibit outstanding activity oxidation sulfides. Within 6 h, methyl phenyl sulfide be quantitatively converted into sulfoxide. in-depth mechanism reveals there also synergistic energy-transfer pathway catalytic system addition electron-transfer pathway. In addition, corresponding well maintained after at least cycle experiments.

Язык: Английский

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