Switching the memory behaviour from binary to ternary by triggering S₆²⁻ relaxation in polysulfide-bearing zinc–organic complex molecular memories

Materials Horizons, Год журнала: 2023, Номер 10(7), С. 2535 - 2541

Опубликована: Янв. 1, 2023

The use of crystalline metal-organic complexes with definite structures as multilevel memories can enable explicit structure-property correlations, which is significant for designing the next generation memories. Here, four Zn-polysulfide different degrees conjugation have been fabricated memory devices. ZnS6(L)2-based (L = pyridine and 3-methylpyridine) exhibit only bipolar binary performances, but ZnS6(L)-based 2,2'-bipyridine 1,10-phenanthroline) illustrate non-volatile ternary performances high ON2/ON1/OFF ratios (104.22/102.27/1 104.85/102.58/1) yields (74% 78%). Their ON1 states stem from packing adjustments organic ligands upon injection carriers, ON2 are a result ring-to-chain relaxation S62- anions. lower conjugated in ZnS6(L)2 less compact packing; consequently, adjacent rings too long to trigger relaxation. deep correlation this work provides new strategy implementing by triggering polysulfide based on degree regulation ligands.

Язык: Английский

---

Effect of Coordination Environment and Electronic Coupling on Redox Entropy in a Family of Dinuclear Complexes

ACS electrochemistry., Год журнала: 2025, Номер unknown

Опубликована: Фев. 18, 2025

Язык: Английский

---

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

JACS Au, Год журнала: 2024, Номер 4(2), С. 771 - 787

Опубликована: Фев. 7, 2024

A series of six binuclear Co(II)-thiolate complexes, [Co

Язык: Английский

---

Transition Metal Mediated Hydrolysis of C–S Bonds: An Overview of a New Reaction Strategy

ACS Organic & Inorganic Au, Год журнала: 2023, Номер 3(6), С. 332 - 349

Опубликована: Сен. 20, 2023

Desulfurization of organosulfur substrates is highly important due to its relation with the industrial hydrodesulfurization (HDS) process fossil fuels, which helps eliminate sulfur-containing impurities such as thiols, sulfide, thiophenes, etc. from crude oil for production easily processed and more cleanly combusted fuel very low sulfur content. While HDS involves a hydrogenolysis reaction under high pressure hydrogen gas at temperature, hydrolysis C–S bonds ambient conditions may well be considered potential alternative model desulfurization reactions. However, unlike availability an appreciable number reports on base, acid, metal ion mediated thioesters in literature, difficult thiolates, sulfides, other remained unavailable until 2017. The recent discovery transition conditions, however, has rapidly filled this gap within past few years. Development new stoichiometric allowed large substrates, including aliphatic aromatic thiocarboxylic acids, disulfides, dibenzothiophene, was subsequently converted catalytic thiols. A brief overview strategy, proposed mechanism, critical analysis efficiency, future prospects are presented.

Язык: Английский

---

Redox Convergent Synthesis and Reactivity of a Cobalt(III)‐Pentasulfido Compound

Chemistry - A European Journal, Год журнала: 2023, Номер 29(32)

Опубликована: Апрель 3, 2023

A new mononuclear cobalt(III)-pentasulfido compound, [(L)Co(S5 )] (3) has been synthesized by using a convergent redox reaction between elemental sulfur and two cobalt(II)-thiolato compounds, [(L)Co(SR)] (R=Ph, 2 a; 2,6-Me2 -C6 H4 , b), which in turn were from dimeric cobalt(II) complex, [(L)2 Co2 ]2+ (1). Compound 3 features low-spin, diamagnetic, Co(III) center with coordinated pentasulfido (S52- ) chain no precedence the literature. is highly stable towards reduction potential of -1.36 V (vs. Cp2 Fe+ /Cp2 Fe) gives back 1 upon chemical/electrochemical reduction. Reaction phosphines yields phosphine sulfides, while protonation S52- leads to formation 1, H2 S. Finally, transfer selected organic such as MeI, PhCH2 Br PhCOCl, for generation organopolysulfido compounds demonstrated.

Язык: Английский

---

Hydrolysis and Transfer Reactivity of the Coordinated Thiolate, Thiocarboxylate, and Selenolate in Binuclear Zinc(II) Complexes

Inorganic Chemistry, Год журнала: 2023, Номер 62(28), С. 11095 - 11111

Опубликована: Июль 6, 2023

A new binuclear Zn(II) complex, [Zn2(PhBIMP)(DMF)2]3+ (1) (where PhBIMP1 is the anion of 2,6-bis[bis[(N-1-methyl-4,5-diphenylimidazoylmethyl)amino]methyl]-4-methylphenol), has been shown for first time to mediate hydrolytic C-S bond cleavage a series aliphatic and aromatic thiolates yield corresponding alcohols/phenols along with formation hydrosulfide-bridged [Zn2(PhBIMP)(μ-SH)(DMF)]2+ (2), which thoroughly characterized in comparison chloride [Zn2(PhBIMP)(Cl)(DMF)]2+ (3), as control. The Zn(II)-thiolate complexes [Zn2(PhBIMP)(μ-SR)]2+ (R = Ph, 4a; 3-Br-C6H4, 4b) have also synthesized by avoiding reaction. Based on experimental results effects H2O Et3N 1, 4a, 4b, complex [Zn2(PhBIMP)(μ-SR)(OH)]1+ proposed be active intermediate that precedes thiolates. [Zn2(PhBIMP)(μ-SCOPh)(DMF)]2+ (5) demonstrates hydrolysis coordinated thiobenzoate produce [Zn2(PhBIMP)(μ-O2CPh)(MeCN)]2+ (6). However, unlike 4a 5, benzeneselenolate-bridged [Zn2(PhBIMP)(μ-SePh)]2+ (7), does not generate species, [Zn2(PhBIMP)(μ-SePh)(OH)]1+, solution, line that, benzeneselenolate 7 undergo hydroselenide phenol. Finally, comparative study transfer reactivity bridging -SH, -SPh, -SC(O)Ph, -SePh ligands 2, 7, respectively, toward selected organic substrates performed reveal distinct differences these ligands.

Язык: Английский

---

Nonheme binuclear transition metal complexes with hydrosulfide and polychalcogenides

Chemical Communications, Год журнала: 2024, Номер 60(38), С. 4979 - 4998

Опубликована: Янв. 1, 2024

An overview of the synthetic methods, structural properties, and reactivity nonheme binuclear first-row transition metal complexes featuring hydrosulfide polychalcogenides is presented.

Язык: Английский

---

Sulfane Decreases the Nucleophilic Reactivity of Zinc Thiolates: Implications for Biological Reactive Sulfur Species

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(45), С. 20630 - 20640

Опубликована: Ноя. 3, 2022

A zinc dithiolate complex supported by a [N3S2] ligand was studied as model for zinc-mediated thiolate-disulfide exchange, enabling isolation of zinc-bound mixed-disulfide intermediate. Solution-phase characterization this zinc-disulfide indicates an interaction between the center and disulfide moiety that results in activation S–S bond subsequent reactions. Comparison reaction with exchange previously prepared tetrasulfanido demonstrates sulfane sulfur (S0) acts efficient thiolate trapping agent, is, polysulfanide anions are much less basic than thiolates. The resulting also exhibit decreased nucleophilicity compared to parent anions. Alkylation kinetics comparisons complexes indicate attenuation sulfane. These suggest general interplay zinc, sulfane, thiol/thiolate reactivity can significantly impact biological redox processes.

Язык: Английский

---

Structural and Redox Interconversions of Sulfur Ligands of Transition Metal Complexes

Comments on Inorganic Chemistry, Год журнала: 2023, Номер 44(2), С. 55 - 97

Опубликована: Апрель 20, 2023

The interactions between transition metals and sulfur have long been studied for potential applications in catalysis energy storage due to the relevance of these motifs biological geological systems. Complexes with sulfur-containing ligands can undergo redox transformations centered on as well at metal. Sulfur also readily catenates other centers form polysulfur motifs. Here, synthesis structures notable examples metal complexes (sulfido, polysulfido, polysulfanido) are described. Aspects sulfur-centered redox, including spectroscopic structural considerations, future research opportunities highlighted.

Язык: Английский

---

Reduction of nitrite to nitric oxide and generation of reactive chalcogen species by mononuclear Fe(ii) and Zn(ii) complexes of thiolate and selenolate

Dalton Transactions, Год журнала: 2023, Номер 53(3), С. 949 - 965

Опубликована: Дек. 11, 2023

Comparative reactivity of a series new Zn(II) and Fe(II) compounds, [(Py2ald)M(ER)] (E = S, R Ph: M Zn, 1aZn; Fe, 1aFe; E 2,6-Me

Язык: Английский

---