Exploration and Insights on Topology Adjustment of Giant Heterometallic Cages Featuring Inorganic Skeletons Assisted by Machine Learning

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(42), С. 23188 - 23195

Опубликована: Окт. 11, 2023

Inorganic molecular cages are emerging multifunctional molecular-based platforms with the unique merits of rigid skeletons and inherited properties from constituent metal ions. However, sensitive coordination bonds vast synthetic space have limited their systematic exploration. Herein, two giant cage-like clusters featuring organic ligand-directed inorganic Ni4[La74Ni104(IDA)96(OH)184(C2O4)12(H2O)76]·(NO3)38·(H2O)120 (La74Ni104, 5 × 3 - C2O4) [La84Ni132(IDA)108(OH)168(C2O4)24(NO3)12(H2O)116]·(NO3)72·(H2O)296 (La84Ni132, were discovered by a high-throughput search. With assistance machine learning analysis experimental data, phase diagrams in four-parameter depicted. The effect alkali, oxalate, other parameters on formation mechanism regulating size n m l elucidated. This work uses synthesis methods to improve efficiency 3d-4f cluster discovery finds highest-nuclearity date through oxalate ions, which pushes methodology study elusive significantly way.

Язык: Английский

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Selective Construction of Borromean Rings and Tweezer‐Like Molecular Assembly Featuring Cp*Rh/Ir Clips for Near‐Infrared Photothermal Conversion^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(23), С. 3229 - 3237

Опубликована: Июль 19, 2023

Comprehensive Summary Making full use of coordination‐driven self‐assembly strategy, we herein described the selective synthesis a molecular Borromean rings and two cases “U”‐shaped tweezer‐like assemblies in high yield by using bipyridyl ligands based on biphenyl unit half‐sandwich binuclear rhodium(III)/iridium(III) building blocks. The was realized adjusting length dipyridyl arms. utilization curved U‐shaped ligand L1 led to assemblies. Subsequently, olefinic bonds were introduced elongate arms obtaining L2 . has stable conformations, U‐shape Z‐shape, which facilitated formation different topologies including tetranuclear macrocycle with blocks this work. These structures solid solution all have been further confirmed single‐crystal X‐ray diffraction, NMR analysis, mass spectrometry. In addition, as an important driving force, π‐π stacking interactions not only played significant role stability but also triggered photothermal conversion solution. experimental results demonstrated that compounds 1a 2 had good NIR efficiency (11.83% 17.76%), analysis found gradual increase trend increasing. This research expands application topological materials science provides new idea for novel materials.

Язык: Английский

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Size-controlled synthesis and near-infrared photothermal response of Cp* Rh-based metalla[2]catenanes and rectangular metallamacrocycles

Chinese Chemical Letters, Год журнала: 2023, Номер 35(6), С. 109298 - 109298

Опубликована: Ноя. 13, 2023

Язык: Английский

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A strategy for regioselective B–H functionalization ofo-carboranesviabase metal catalysis

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(12), С. 3074 - 3079

Опубликована: Янв. 1, 2023

This frontier article summarizes the recent developments in base metal-catalyzed regioselective cage B–H functionalization of carboranes and discusses related challenging issues.

Язык: Английский

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Nickelacarborane-Supported Bis-N-heterocyclic Carbenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15538 - 15546

Опубликована: Июль 6, 2023

Metallacarboranes have attracted significant attention due to their unique properties. Considerable efforts been made on the reactions around metal centers or ion itself, while transformations of functional groups metallacarboranes much less explored. We presented here formation imidazolium-functionalized nickelacarboranes (2), subsequent conversion nickelacarborane-supported N-heterocyclic carbenoids (NHCs, 3), and reactivities 3 toward Au(PPh3)Cl Se powder, which resulted in bis-gold carbene complexes (4) NHC selenium adducts (5). Cyclic voltammetry 4 shows two reversible peaks, corresponding interconversion NiII ↔ NiIII NiIV. Theoretical calculations demonstrated relatively high-lying lone-pair orbitals, weak B-H···H-C interactions between BH units methyl group, B-H···π vacant p-orbital carbene.

Язык: Английский

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Formation and reactivity of a unique M⋯C–H interaction stabilized by carborane cages

Chemical Science, Год журнала: 2024, Номер 15(24), С. 9274 - 9280

Опубликована: Янв. 1, 2024

Broadening carborane applications has consistently been the goal of chemists in this field. Herein, compared to alkyl or aryl groups, a cage demonstrates an advantage stabilizing unique bonding interaction: M⋯C–H interaction.

Язык: Английский

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Synthesis, structural diversity, and methanol vapor adsorption properties of three Hg(II) halide complexes derived from a helical Schiff base

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The Schiff base condensation reaction between precursor diamine N,N'-bis(2-aminophenyl)-pyridine-2,6-dicarboxamide and 1,8-naphthyridine-2-carbaldehyde yielded a racemic compound (L^P/L^M), which was characterized by ¹H/¹³C NMR, infrared spectroscopy, elemental analysis, single crystal X-ray diffraction. Three complexes, [Hg₂LI₄] (1), [Hg₂LBr₄] (2), [Hg₂L₂Cl₄]‧2H₂O (3) with different coordination configurations were obtained from the of this HgX₂ (X = I⁻, Br⁻, Cl⁻), respectively, their structures geometries determined via diffraction techniques. Both 1 2 exist as dinuclear complexes 1:2 molar ratio L Hg(II), while 3 exists 44-membered metallamacrocycle 1:1 Hg(II). structural diversity these three indicates that counter anions have significant effects on topology. In addition, solid-state luminescence gas adsorption towards methanol vapor at room temperature investigated.

Язык: Английский

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Palladium-Catalyzed Cross-Coupling Reactions of Carboranes with Alkenes via Selective B–H Bond Activation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

A palladium-catalyzed Heck-type cross-coupling reaction of carboranes with alkenes in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was realized. This shows good B(9) selectivity for m-carboranes and is also suitable o- p-carborane. Meanwhile, a series mono-, di-, trisubstituted were compatible substrates to afford the alkenylated products 16–89% yields. The 1,2-bis(carboranyl)ethylene first synthesized by vinyltrimethylsilane m-carborane. Further transformations C═C bond product examined hydroboration oxidation, hydroboration, bromination generate corresponding B(9)-functionalized m-carboranes.

Язык: Английский

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Post-coordination of Ru(II) Controlled Regioselective B(4)–H Acylmethylation of o-Carboranes with Sulfoxonium Ylides

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Despite significant progress in the B-H functionalization of carboranes, development cost-effective catalytic systems devoid noble metals, coupled with mechanistic validation regioselectivity control, remains a formidable challenge. Herein, we disclose an Ag salt-free, redox-neutral, and inexpensive ruthenium(ii)-catalyzed protocol that enables exclusive B(4)-H acylmethylation o-carboranes through novel post-coordination strategy. By exploiting weakly coordinating carboxylic acid as traceless directing group, this method achieves excellent mono-site selectivity for B-C(sp3) bond formation using diverse sulfoxonium ylides, demonstrating both functional group tolerance synthetic scalability. This work not only establishes practical platform but also addresses critical questions unresolved prior analogous studies. Through deuterium labeling, situ high-resolution mass spectrometry (HRMS) tracking, single-crystal X-ray analysis Ru intermediates, unequivocally demonstrate originates from unique mode Ru(ii). The catalyst simultaneously engages enolizable acylmethyl moiety mono-acylated intermediate, thereby dictating activation trajectory. Our findings establish generalizable regiocontrolled carborane while defining paradigms transition metal-mediated chemistry.

Язык: Английский

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A Pd(II) → Pd(0) → Pd(II) Catalytic Cycle Enables the Generation of Bis(o-carborane)s: Confirmed by Reproduced Yields and Ratios, Regioselectivities, Additive and Substituent Effects

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

The palladium-catalyzed generation of bis(o-carborane)s via regioselective B-B coupling was explored by using density functional theory (DFT). It is found that the reaction proceeds through sequential B4-H activation, B4'-H/B5'-H and reductive elimination, yielding ultimately. palladium catalyst tends to experience a Pd(II) → Pd(0) rather than Pd(IV) catalytic cycle, in which second B-H (B4'-H/B5'-H) activation serves as rate-determining step (RDS). Computed RDS step's barriers (27.0/29.0 kcal·mol-1, TS2a_I/TS2a'_I) consist well with experimental yields selectivities (P1a:P2a = 57%:23%). regioselectivity primarily controlled process, electronic effect playing key role steric hindrance influencing somewhat, confirmed natural bond orbital (NBO) noncovalent interaction (NCI) analyses. free-energy (27.0/29.6/31.1 kcal·mol-1) for AgOAc/AgF/NiCl2-co-assisted (Path a_I), AgOAc/AgF-co-assisted a_II), AgOAc-assisted a_III) cases agree perfectly corresponding trends (obtained 57%/43%/12% P1a, respectively). Theoretical predictions substituent effects also demonstrate consistency observations. This perfect agreement between experiments computations validates providing crucial insights into o-carboranes thus aiding controllable synthesis carborane materials.

Язык: Английский

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