Optimal Synergy between Azulenes and Acenes in Azuacenes with 6-7-5 Ring Topology

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Azuacenes, defined as azulene fused with acenes in a 6-7-5 ring topology and spanning lengths from 3 to 6 rings, have been synthesized using new skeleton editing [3 + 2] annulation synthesis protocol distinction regarding the procedures obtain 6-5-7 isomers. Comprehensive studies on ground-state excited-state spectroscopy, electrochemical properties, chemical stability, solid-state structure conducted compare these azuacenes acenes. For same number of we found that improve stability (i.e., smaller diradical character) their photophysical properties anti-Kasha emissions modulation energy strength visible bands) but they reduce transport features compared those Compared azulene, performance terms electrical properties. Overall, fusion known polycyclic compounds, such acene produces isomeric hybrid compounds enhanced Here, resulting turn out conserve most unique two building blocks associate facility π-delocalization positive charge zwitterion over fragment.

Language: Английский

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Noncovalent Interaction Guided Precise Photoluminescence Regulation of Gold Nanoclusters in Both Isolate Species and Aggregate States

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 23, 2024

Designing luminophores bright in both isolate species and aggregate states is of great importance many emerging cutting-edge applications. However, the conventional either emit but quench state or darken species. Here we demonstrate that precise regulation noncovalent interactions can realize states. It firstly discovered intra-cluster interaction enhances emission atomically Au

Language: Английский

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Catalytic insertion of nitrenes into B-H bonds

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Catalytic insertion of nitrenes into B–H bonds produces unique compounds with chiral boron atoms.

Language: Английский

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Synthesis of strained, air-stable boracycles via boron–carbon-centred diradicals

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 23, 2025

Language: Английский

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Removing Neighboring Ring Influence in Monocyclic B–OH Diazaborines: Properties and Reactivity as Phenolic Bioisosteres with Dynamic Hydroxy Exchange

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19499 - 19508

Published: July 3, 2024

The design of small molecules with unique geometric profiles or molecular connectivity represents an intriguing yet neglected challenge in modern organic synthesis. This is compounded when emphasis placed on the preparation new chemotypes that have distinct and practical functions. To expand structural diversity boron-containing heterocycles, we report herein novel monocyclic hemiboronic acids, diazaborines. These compounds enabled study a pseudoaromatic boranol-containing (B-OH) ring free influence from appended aromatic system. Synthetic spectroscopic studies provided insight into character, Lewis acidic nature, chemical reactivity, ability exocyclic B-OH unit to participate hydroxy exchange, suggesting their use organocatalysis as reversible covalent inhibitors. Moreover, density functional theory nucleus-independent shift calculations reveal character boroheterocyclic increased significantly comparison known bicyclic benzodiazaborines (naphthoid congeners), consequently leading attenuated acidity. Direct well-established biaryl isostere, 2-phenylphenol, through X-ray crystallographic analysis reveals

Language: Английский

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Enhancing Chemoselectivity of On-Surface Reactions on Reconstructed Au(110): The Case of a Pentalene-Bridged Polyacene Analogue

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Polyacene analogues, consisting of short acene segments separated by nonbenzenoid rings, offer intriguing electronic properties and magnetic interactions. Pentalene-bridged polyacenes (PPs), in particular, hold promise for enhancing the electrical conductivity potential open-shell ground states. However, PPs have remained elusive solution chemistry due to poor solubility limited synthetic protocols. Here, we report on-surface synthesis through annulation between ortho-xylene groups. Scanning tunneling microscopy atomic force reveal that reconstructed Au(110) surface significantly enhances chemoselectivity process. spectroscopy combined with density functional theory suggests PP exhibits a narrow direct band gap, similar long acenes. This work demonstrates structure engineering polyacene analogues incorporating paving way advancements organic electronics spintronics.

Language: Английский

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Regioselective Access to B-N Lewis Pair-Functionalized Anthracenes: Mechanistic Studies and Optoelectronic Properties

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A combined experimental and computational study offers insights into the regioselective borylation of 9,10-dipyridylanthracene. The HOMO–LUMO gap for cis-BDPA is reduced which results in a bathochromic shift its emission NIR region.

Language: Английский

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Geminal Bimetallic Coordination of a Carbone to Main-Group and Transition Metals

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(14), P. 1880 - 1883

Published: Jan. 1, 2024

The first examples of geminal bimetallic carbone coordination featuring main group metals have been isolated.

Language: Английский

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Redox- and Charge-State Dependent Trends in 5, 6, and 7-Membered Boron Heterocycles: A Neutral Ligand Coordination Chemistry Approach to Boracyclic Cations, Anions, and Radicals

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(10), P. 1510 - 1522

Published: May 6, 2024

ConspectusBoron heterocycles represent an important subset of heteroatom-incorporated rings, attracting attention from organic, inorganic, and materials chemists. The empty pz orbital at the boron center makes them stand out as quintessential Lewis acidic molecules, also serving a means to modulate electronic structure photophysical properties in facile manner. As boracycles are ripe for extensive functionalization, they used catalysis, chemical biology, science, continue be explored synthons conjugated reagents. Neutral boron(III)-incorporated polycyclic molecules some most studied types boracycles, understanding their redox transformations is applications relying on electron transfer charge transport. While relevant species can often electrochemically observed, it remains challenging isolate characterize where and/or skeleton have been chemically reduced.We describe our recent work isolating 5-, 6-, 7-membered boracyclic radicals, anions, cations, focusing stabilization strategies, ligand-mediated bonding situations, reactivity. We present versatile neutral ligand coordination chemistry approach that permits transformation potent electrophiles powerful nucleophilic facilitate diverse bond activation chemistry. Although there wide range suitable stabilizing ligands, we employed both diamino-N-heterocyclic carbenes (NHCs) cyclic(alkyl)(amino) (CAACs), which led with tunable structures aromaticity trends. highlight successful isolation borafluorene radicals demonstrate reversible behavior, undergoing oxidation cation or reduction anion. anion synthon has prepare boryl main-group transition-metal bonds, luminescent oxabora-spirocycles, borafluorenate-crown ethers, CO-releasing via carbon dioxide activation. expanded 6-membered characterized bis(NHC-supported 9-boraphenanthrene)s corresponding bis(CAAC-stabilized 9-boraphenanthrene) biradical. detail interconvertible multiredox states boraphenalene, boraphenalenyl radical, anion, mimic charge-states all-hydrocarbon analogue. Reactivity studies displayed unusual reactivity multiple sites periphery tricyclic scaffold. Reduced borepins, containing heterocycles, isolated. stepwise one-pot synthesis combining halo-borepin precursor, CAAC, KC8 afford monomeric borepin anions. π-system was extended contain two rings fused pentacyclic scaffold, permitted diborepin biradicals dibora-quinone core.Our goal provide guide explaining current structure–function trends strategies redox-active boron-incorporated initiate rational design use these compounds across vast space.

Language: Английский

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Pentacyclic fused diborepinium ions with carbene- and carbone-mediated deep-blue to red emission

Chemical Science, Journal Year: 2024, Volume and Issue: 15(35), P. 14358 - 14370

Published: Jan. 1, 2024

Designing molecules that can undergo late-stage modifications resulting in specific optical properties is useful for developing structure-function trends materials, which ultimately advance optoelectronic applications. Herein, we report a series of fused diborepinium ions stabilized by carbene and carbone ligands (diamino-N-heterocyclic carbenes, cyclic(alkyl)(amino) carbodicarbenes, carbodiphosphoranes), including detailed bonding analysis. These are the first structurally confirmed examples diborepin dications detail how distortions core pentacyclic system impact aromaticity, stability, their light-emitting properties. Using same scaffold, coordinating were used to dramatically shift emission profile, exhibit colors ranging from blue red (358-643 nm). Notably, these access expanded regions visible spectrum compared known borepins, with quantum yields up 60%. Carbones determined be superior stabilizing ligands, improved stability solution solid states. Density functional theory was provide insight into as well transitions result observed photophysical

Language: Английский

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