Gold–Manganese Bimetallic Redox Coupling with Light

Xia, Siyu; Li, Weipeng; Chen, Hongliang; Zhu, Chengjian; Han, Jie; Xie, Jin

doi:10.1021/jacs.3c08796

Cited by 4 publications

(3 citation statements)

References 75 publications

(85 reference statements)

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“…À counter ion is detected by its 19 F and 31 P NMR resonances as well as its characteristic IR frequencies (Figures S3, S4 and S9).…”

Section: Resultsmentioning

confidence: 99%

“…Suitable environments to prevent disproportionation or dimerization are gas phase conditions in the mass spectrometer, [8] noble gas matrices [9][10][11] or zeolite encapsulation for a kinetic stabilization of mononuclear gold(II) species. [12] Transient gold(II) species have also been proposed as intermediates in homogenous catalysis, [2,[13][14][15][16][17][18][19] artificial photosynthesis systems [20][21][22] or radical [23][24][25][26] and PCET [27,28] chemistry. In solid state materials, such as in simple salts AuCl 2 or AuSO 4 , either a mixed-valence situation Au I Au III Cl 4 or dimerization [Au II (SO 4 )] 2 occurs.…”

Section: Introductionmentioning

confidence: 99%

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14‐Membered Macrocyclic β‐Diiminato Gold(II) – A New Member for the Gold(II) Complex Family?

Sorge,

Link,

Heinze

2024

Chemistry A European J

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The chemistry of molecular gold compounds is dominated by the oxidation states +I and +III. For the intermediate oxidation state +II with 5d9 electron configuration, dimerization or disproportionation of the gold(II) radicals is favoured, so that only a few mononuclear gold(II) complexes have been isolated to date. The present study addresses the one‐electron reduction of the macrocyclic gold(III) complex [AuIIIL]+ of the innocent β‐diketiminato ligand L2– with a 14membered macrocycle (L2– = 5,7,12,14‐tetramethyl‐1,4,8,11tetraazacyclotetradeca‐5,7,12,14‐tetraenato). Electrochemistry, spectroelectrochemistry and chemical reduction of [AuIIIL]+ monitored by UV/Vis, NMR and EPR spectroscopy together with density functional theory calculations reveal disproportionation of the initially generated but elusive gold(II) complex AuIIL and provide guidelines for prospective stable mononuclear tetraazamacrocyclic gold(II) complexes.

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“…À counter ion is detected by its 19 F and 31 P NMR resonances as well as its characteristic IR frequencies (Figures S3, S4 and S9).…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

14‐Membered Macrocyclic β‐Diiminato Gold(II) – A New Member for the Gold(II) Complex Family?

Sorge,

Link,

Heinze

2024

Chemistry A European J

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“…The pursuit of photocatalysts derived from Earth-abundant elements, especially targeting first-row 3d transition metals to enhance both reaction efficiency and selectivity, has burgeoned into a thriving domain within synthetic chemistry. − These elements stand as sustainable alternatives to conventional noble metals like iridium and ruthenium, while also facilitating the creation of innovative catalysts with unique reactivity and excited-state characteristics. Among them, manganese, ranking as the third most abundant transition metal following iron and titanium, attracts intense interest for its low toxicity and eco-friendly attributes. − Its capacity to adopt a broad spectrum of oxidation states, ranging from −3 to +7, intimates at a wealth of possible excited states and substantial photocatalytic potential. , Nonetheless, an inherent challenge posed by first-row transition metals, manganese included, revolves around their tightly packed 3d electron configurations, which hinder effective ligand interactions compared to the more expansive 4d or 5d orbitals of heavier metals. This characteristic accelerates the quenching of excited states, leaving manganese complexes often plagued by a diminished light responsiveness. , …”

Section: Introductionmentioning

confidence: 99%

Manganese Complexes with Consecutive Mn(IV) → Mn(III) Excitation for Versatile Photoredox Catalysis

Huang,

Du,

Cheng

et al. 2024

J. Am. Chem. Soc.

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Manganese complexes stand out as promising candidates for photocatalyst design, attributed to their eco-and biocompatibility, versatile valence states, and capability for facilitating multiple electronic excitations. However, several intrinsic constraints, such as inadequate visible light response and short excited-state lifetimes, hinder effective photoinduced electron transfer and impede photoredox activation of substrates. To overcome this obstacle, we have developed a class of manganese complexes featuring boron-incorporated N-heterocyclic carbene ligands. These complexes enable prolonged excited-state durations encapsulating both Mn(IV) and Mn(III) oxidation stages, with lifetimes reaching microseconds for Mn(IV) and nanoseconds for Mn(III), concurrently exhibiting robust redox capabilities. They efficiently catalyze direct, site-selective cross-couplings between diverse arenes and aryl bromides, at a low catalyst loading of 0.5 mol %. Their proficiency spans an extensive array of substrates including both highly electron-rich and electron-deficient molecules, which underscore the superior performance of these manganese complexes in tackling intricate transformations. Furthermore, the versatility of these complexes is further highlighted by their successful applications in various photochemical transformations, encompassing reductive cross-couplings for the formation of C−P, C−B, C−S and C−Se bonds, alongside oxidative couplings for creating C−N bonds. This study sheds light on the distinctive photoredox properties and the remarkable catalytic flexibility of manganese complexes, highlighting their immense potential to drive progress in photochemical synthesis and green chemistry applications.

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Microenvironment‐Responsive Targeted Nanomedicine for a Collaborative Integration of Tumor Theranostics and Bone Defect Repair

Wang,

Kang,

Zhang

et al. 2024

Adv Healthcare Materials

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Despite advancements in breast cancer treatment, bone metastases remain a significant concern for patients with advanced breast cancer. Current theranostics strategies face challenges in integrating tumor theranostics and bone formation. Herein, we developed an activatable targeted nanomedicine AuMnCO@BSA‐N3 (AMCBN) to enable a novel collaborative integration of second near‐infrared (NIR‐II) fluorescence imaging guided precise theranostics for breast cancer bone metastases and osteogenic microenvironment remolding. This strategy employed a chemical coordination between noble metal complex and metal carbonyl (MnCO). The surface modification of azide groups for enhanced tumor affinity through passive and active targeting. The initiated respondent behavior of AMCBN by tumor microenvironment (H2O2/acidity) accelerate the degradation of coordinated MnCO, resulting in a rapid release of multifunctional agents for efficient chemodynamic therapy (CDT)/gas synergistic therapy. Meanwhile, the exceptional bone‐binding properties enable the efficient and controlled release of Mn2+ ions and CO in the bone microenvironment, thereby facilitating the expression of osteogenesis‐related proteins and establishing a novel synchronous theranostics process for tumor‐bone repair.This article is protected by copyright. All rights reserved

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Gold–Manganese Bimetallic Redox Coupling with Light

Cited by 4 publications

References 75 publications

14‐Membered Macrocyclic β‐Diiminato Gold(II) – A New Member for the Gold(II) Complex Family?

14‐Membered Macrocyclic β‐Diiminato Gold(II) – A New Member for the Gold(II) Complex Family?

Manganese Complexes with Consecutive Mn(IV) → Mn(III) Excitation for Versatile Photoredox Catalysis

Microenvironment‐Responsive Targeted Nanomedicine for a Collaborative Integration of Tumor Theranostics and Bone Defect Repair

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