Gilliard Group

Redox- and Protonation-Tunable Diboraheptacenes (@judywuchem.bsky.social, @rjgilliard.bsky.social, @gilliardgroup.bsky.social): pubs.acs.org/doi/10.1021/... (@jacs.acspublications.org).

Redox- and Protonation-Tunable Diboraheptacenes Acenes are attractive molecular platforms with characteristic π-electron delocalization, resulting in exceptionally small HOMO–LUMO gaps, which makes them valuable for use in a variety of organic elec...

Our manuscript on the redox- and protonation-chemistry of diboraheptacenes is published in @jacs.acspublications.org (pubs.acs.org/doi/full/10....)! @JinhyoHwang and @chemheechan report a DBH dianion (w/NIR absorption) that’s the longest fully conjugated boron-doped acene! #maingroup

Diboron- and digermanium-doped dihydrodibenzohexacenes: Ge–B exchange to access boron-doped extended acenes ( @gilliardgroup.bsky.social, @cromeronieto.bsky.social) : pubs.rsc.org/en/content/a... ( @chemicalscience.rsc.org ).

Borenium Ions as Functional Materials Borenium ions are tricoordinate boron cations of the type [LBR2]+, where L is a donor ligand. While the inherently reactive nature of these Lewis acidic species has been harnessed to advance bond acti...

Check out Nathan's article in @jacs.acspublications.org on luminescent and stimuli-responsive borenium ion materials! #maingroup pubs.acs.org/doi/10.1021/...

Chemists create red fluorescent dyes that may enable clearer biomedical imaging MIT chemists designed a fluorescent molecule they hope could be used for applications such as generating clearer images of tumors. The dye is based on a borenium ion — a positively charged form of bor...

MIT News covers Chunlin's new paper in @natchem.nature.com! news.mit.edu/2025/chemist...

Our manuscript detailing the impact of carbene ligands on the synthesis, properties, and reactivity of 8 diazoboranes is now published in JACS (pubs.acs.org/doi/10.1021/...)! Take a look at the unusual boraketenes and diazaborles! #maingroup #boron @jacs.acspublications.org

After our 2025 Research Retreat where we discussed our research plans for the academic year, we had a nice dinner at
Lucca in Boston!

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