Gilliard Group

From @heechankim.bsky.social @rjgilliard.bsky.social a range of boron helices @jacs.acspublications.org.

This double-stranded diborahelicate could be transformed into luminescent borahelicates and cationic boron coordination complexes.

🔗 CSD Entry CABXAJ: bit.ly/46xskm6

#FeaturedStructureFriday

For #FluorescenceFriday we share @heechankim.bsky.social’s new work in JACS on cationic boron helicates and helicenes! 🔥🔥🔥 #luminescence #boron #chiral #maingroup pubs.acs.org/doi/10.1021/... @jacs.acspublications.org

Coordination Chemistry Meets Boron Helices: Cationic Double-Stranded Diborahelicates and Bora[7]helicenes with Multicolor Emission | Journal of the American Chemical Society pubs.acs.org/doi/full/10....

Our manuscript on cationic double-stranded diborahelicates and borahelicenes is now published in JACS @jacs.acspublications.org (pubs.acs.org/doi/10.1021/...)! Heechan reports borahelices with multicolor emission and high absorption dissymmetry factors! @gilliardgroup.bsky.social #maingroup

Unlocking the Ambiphilicity of the Boryl Anion: Synthesis and Reactivity of an Anionic Diazoborane (@rjgilliard.bsky.social , @gilliardgroup.bsky.social): pubs.acs.org/doi/10.1021/... (@jacs.acspublications.org).

Our manuscript on unlocking the ambiphilicity of boryl anions is now published in JACS @jacs.acspublications.org (pubs.acs.org/doi/full/10....)! Chonghe, Junyi, Xibao, and coworkers report the synthesis and reactivity of the first anionic diazoborane! #maingroup #boron @gilliardgroup.bsky.social

Unlocking the Ambiphilicity of the Boryl Anion: Synthesis and Reactivity of an Anionic Diazoborane Reported boryl anions (R2B–) often exhibit n–p conjugation between the boron atom and adjacent heteroatoms, with their nucleophilicity being the primary focus. In this work, we present evidence that a...

Unlocking the Ambiphilicity of the Boryl Anion: Synthesis and Reactivity of an Anionic Diazoborane | Journal of the American Chemical Society #maingroup @jacs.acspublications.org pubs.acs.org/doi/full/10....

We are excited to welcome Dr. Gargi Kundu @gargis.bsky.social to our lab as a Fulbright Postdoctoral Fellow!

Hexamethylbenzene Elimination Enables the Generation of Transient, Sterically Unhindered Multiply Bonded Boron Species | @chemicalscience.rsc.org pubs.rsc.org/en/content/a...

Diboron-Incorporated Indenofluorene: Isolation of Crystalline Neutral and Reduced States of 6,12-Diboraindeno[1,2-b]fluorene The synthesis and redox transformations of 6,12-diboraindeno[1,2-b]fluorene (DBIF)─a pentacyclic π-system with diboron incorporation─are reported. In notable contrast to the all-hydrocarbon indenofluo...

Diboron-Incorporated Indenofluorene: Isolation of Crystalline Neutral and Reduced States of 6,12-Diboraindeno[1,2-b]fluorene | @jacs.acspublications.org pubs.acs.org/doi/full/10....

Group lunch at Mex after lab clean-up!

Dicationic Boron Derivatives of Schlenk’s and Thiele’s Hydrocarbon In recent years, neutral NHC-stabilized boryl radicals have been investigated as reactive species in various organic transformations. However, cationic boron radicals have been significantly less explored. In addition, boron-centered open-shell species with S > 1/2 have emerged as attractive synthetic targets. In this study, we provide a synthetic route to an NHC-stabilized boryl radical cation as a salt of the weakly coordinating [Al(ORF)4]− (RF = C(CF3)3) anion. The synthetic procedure was extended to dicationic diboron derivatives of Schlenk’s and Thiele’s hydrocarbons with meta- and para-phenylene coupling units between the spin centers. While most known isolable boron biradicals have a singlet ground-state with a thermally accessible triplet state, the boron version of Schlenk’s hydrocarbon occupies a ground-state triplet spin-state, as shown by combined electron paramagnetic resonance spectroscopy and density functional theory studies. Furthermore, initial reactivity studies of the dications with elemental sulfur and diphenyldiselenide are presented.

Dicationic Boron Derivatives of Schlenk’s and Thiele’s Hydrocarbon | Journal of the American Chemical Society @jacs.acspublications.org @pubs.acs.org

pubs.acs.org/doi/full/10....

Merry Christmas from our lab to you and yours! 🎄

Heechan wins one of the Boron Specialties awards at the BORAM-18 conference!!!

We are really enjoying BORAM-18 at UCLA!!!

Nathan presents his work on new frustrated Lewis pairs and boryl chalcogenides!

Philipp presents his new work on boryl radical cations at BORAM-18!

Heechan presents his new work on multi-boron-doped radicals at BORAM-18!

Chonghe presents his synthesis of a diazoborane at BORAM-18! He isolated the first boron-terminal N2 compound.

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 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 cen...

Redox and Charge State Dependent Trends in Boron Heterocycles: A Neutral Ligand Coordination Chemistry Approach to Boracyclic Cations, Anions, and Radicals | Accounts of Chemical Research #ouryearinreview @gilliardgroup.bsky.social #maingroup #chemsky pubs.acs.org/doi/full/10....

Borafluorene-Mediated Sulfur Activation: Isolation of Boryl-Linked S7 and S8 Catenates and Related Chalcogenide Molecules Although the activation of elemental sulfur by main group compounds is well-documented in the literature, the products of such reactions are often heterocyclic in nature. However, the isolation and ch...

Borafluorene-Mediated Sulfur Activation: Isolation of Boryl-Linked S7 and S8 Catenates and Related Chalcogenide Molecules | Inorganic Chemistry #ouryearinreview @gilliardgroup.bsky.social #maingroup #chemsky pubs.acs.org/doi/10.1021/...

Carbodicarbene‐Stibenium Ion‐Mediated Functionalization of C(sp3)−H and C(sp)−H Bonds A Lewis acidic carbodicarbene-stibenium ion mediates C(sp3)−H and C(sp)−H bond breaking of acetonitrile and terminal alkynes in the presence of an organic base. The resulting adducts were reacted wit...

Carbodicarbene-Stibenium Ion-Mediated Functionalization of C(sp3)−H and C(sp)−H Bonds | Angewandte Chemie #ouryearinreview @gilliardgroup.bsky.social #maingroup #chemsky @angewandtechemie.bsky.social onlinelibrary.wiley.com/doi/10.1002/...

Pentacyclic fused diborepinium ions with carbene- and carbone-mediated deep-blue to red emission Designing molecules that can undergo late-stage modifications resulting in specific optical properties is useful for developing structure-function trends in materials, which ultimately advance optoele...

Pentacyclic Fused Diborepinium Ions with Carbene- and Carbone-Mediated Deep-Blue to Red Emission | Chemical Science pubs.rsc.org/en/content/a... #ouryearinreview @gilliardgroup.bsky.social #chemsky #maingroup #boron @roysocchem.bsky.social

Synthesis and reactivity of an N-heterocyclic carbene–stabilized diazoborane Diazo compounds and organic azides are widely used as reagents for accessing valuable molecules in multiple areas of fundamental and applied chemistry. Their capacity to undergo versatile chemical tra...

NHC-Stabilized Diazoborane (the first isolated boron-terminal N2 species, a borylene transfer reagent) | Science Magazine @science.org #ouryearinreview @gilliardgroup.bsky.social #chemsky #maingroup #boron
www.science.org/doi/10.1126/...

Carbodiphosphorane-Activated Distibene and Dibismuthene Dications Low-valent antimony and bismuth have emerged as novel platforms for achieving reversible small-molecule activation at main-group metals. Although various examples of oxidative addition reactions at mo...

Carbodiphosphorane-Activated Distibene and Dibismuthene Dications | Journal of the American Chemical Society (JACS)
#ouryearinreview @gilliardgroup.bsky.social #chemsky #maingroup pubs.acs.org/doi/10.1021/...

Unlocking Biradical Character in Diborepins Systems that possess open- and closed-shell behavior attract significant attention from researchers due to their inherent redox and charge transport properties. Herein, we report the synthesis of the first diborepin biradicals. They display tunable biradical character based on the steric and electronic profile of the stabilizing ligand and the resulting geometric deviation of the diborepin core from planarity. While there are numerous all-carbon-based biradical systems, boron-based biradical compounds are comparatively rare, particularly ones in which the radical sites are disjointed. Calculations using density functional theory (DFT) and multireference methods demonstrate that the fused diborepin scaffold exhibits high biradical character, up to 95%. Use of a nonsterically demanding diaminocarbene promotes the planarization of the pentacyclic framework, resulting in the synthetic realization of a diborepin containing a dibora-quinoidal core, which possesses a closed-shell ground state and thermally accessible triplet state. The biradicals were structurally authenticated and characterized by both solution and solid-state electron paramagnetic resonance (EPR) spectroscopy. Half-field transitions were observed at low temperatures (about 170 K), confirming the presence of the triplet state. Initial reactivity studies of the biradicals led to the isolation and structural characterization of bis(borepin hydride) and bis(borepin dianion).

Unlocking Biradical Character in Diborepins | Journal of the American Chemical Society (JACS) #ouryearinreview @gilliardgroup.bsky.social #chemsky #maingroup pubs.acs.org/doi/full/10....

Air- and photo-stable luminescent carbodicarbene-azaboraacenium ions - Nature Chemistry Borenium ions have traditionally served as main group (pre-)catalysts, and their use in materials-related applications have been limited by their instability. Now, a series of fully π-conjugated azabo...

Luminescent Carbodicarbene-Azaboraacenium Ions | @naturechemistry.bsky.social #ouryearinreview @gilliardgroup.bsky.social #chemsky #maingroup

www.nature.com/articles/s41...