About

Robert J. Gilliard, Jr. is the Novartis Professor of Chemistry at MIT and serves as the Graduate Officer in the Department of Chemistry. His research is multidisciplinary, combining aspects of organic, inorganic, main-group, and materials chemistry. His laboratory develops novel synthetic methods to access molecules important for solving problems related to the design of stimuli-responsive materials, fluorescent probes, and the discovery of new main-group element chemical synthons. His work includes the activation of energy-relevant small molecules such as carbon dioxide, the design of luminescent organic materials and stimuli-responsive materials, and the synthesis of boron-doped nanographenes and graphene nanoribbons. Gilliard's research also focuses on understanding the impact of main-group heteroatoms on traditional organic PAH materials, as well as bond activation by low-coordinate heavy pnictogens like bismuth and antimony. His contributions include the development of thermoluminescent borafluorenium and borepinium ions, the synthesis of boron-incorporated organic materials, and the exploration of energy-relevant small molecule activation, with applications in biomedical therapies, energy storage, and catalysis. His work is supported by grants from agencies such as the NSF, NIH, and various foundations.

Research topics

• Photochemistry
• Organic chemistry
• Chemistry
• Medicinal chemistry
• Nuclear magnetic resonance
• Crystallography
• Inorganic chemistry
• Stereochemistry

Selected publications

• CCDC 2502459: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-02-27

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• CCDC 2502461: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-02-27

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• Borenium Ions as Functional Materials

  Journal of the American Chemical Society · 2026-02-20 · 1 citations

  articleSenior authorCorresponding

  , where L is a donor ligand. While the inherently reactive nature of these Lewis acidic species has been harnessed to advance bond activation methodologies and catalysis, it has historically limited investigations into the optoelectronic properties of these systems. Borenium ions have the potential to serve as tunable low-energy LUMO materials, but there remains a gap in knowledge concerning the factors that impart stability and the specific optical transitions that mediate their function. This Perspective centralizes the key design principles used to tailor the properties of cyclic borenium ions toward functional luminescent materials applications, with a focus on recent examples from the literature. Design concepts including ligand identity, ring size, heteroatom incorporation, and counteranion selection have been identified as pivotal tools enabling the isolation and discovery of various emissive and stimuli-responsive boron cations. These advancements have resulted in the observation of diverse phenomena, including twisted intramolecular charge transfer (TICT), aggregation-induced emission (AIE), exciton coupling, and thermochromic behavior. The concepts highlighted herein serve as a blueprint for future research in main-group element materials chemistry.

  PublisherDOI

• CCDC 2502462: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-02-27

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• CCDC 2502457: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-02-27

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• CCDC 2502460: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-02-27

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• CCDC 2502458: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-02-27

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• Diboron- and digermanium-doped dihydrodibenzohexacenes: Ge–B exchange to access boron-doped extended acenes

  Chemical Science · 2026-01-01

  articleOpen accessSenior authorCorresponding

  diboron-substituted isomer 8 exhibiting slightly anodically shifted reduction potentials. These results demonstrate that diboron and digermanium doping provides a promising platform for the development of stable, emissive, and redox-active polycyclic aromatic hydrocarbons.

  PublisherOA PDFDOI

• CCDC 2502463: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-02-27

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• Redox- and Protonation-Tunable Diboraheptacenes

  Journal of the American Chemical Society · 2026-02-26 · 1 citations

  articleSenior authorCorresponding

  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 electronics. Incorporating heteroatoms into the backbones of acenes enables systematic tuning of their electronic structures and introduces well-defined sites for redox and protonation chemistry. However, the redox chemistry of boron-doped higher acenes remains poorly understood. Herein, we report the synthesis, structural characterization, and multistate redox and protonation chemistry of a series of diboraheptacenes. Starting from tetrahydrodiboraheptacene (1), the corresponding radical anion (1•–) was generated via one-electron reduction. The fully aromatized diborataheptacene dianion (22–) was accessed via double deprotonation, which represents the first diboron-doped π-isostere of all-hydrocarbon heptacene. Two-electron oxidation of 22– gave a neutral quinodimethane (2) that is isoelectronic with the heptacene dication, demonstrating redox-interconversion between benzenoid and quinoidal structures. Dianion 22–, isoelectronic to heptacene, features NIR absorption at λabs = 951 nm, reflecting its exceptionally small HOMO–LUMO gap. In addition, 2 shows remarkable low-energy electronic transitions, displaying red fluorescence (λem = 682 nm). Furthermore, reactions of 22– with CO2 or acrylonitrile yield cycloaddition products, while the reaction with H2O affords a hydroxylated diboraheptacene dianion. These results establish redox- and protonation-state-dependent electronic structures, photophysical properties, and reactivity of an extended diboraacene platform.

  PublisherDOI

Recent grants

• MRI: Acquisition of a Single Crystal X-ray Diffractometer at the University of Virginia

  NSF · $274k · 2020–2023

• CAREER: Boracycles with Unusual Bonding as Creative Strategies for Main-Group Functional Materials

  NSF · $685k · 2021–2023

Frequent coauthors

• Diane A. Dickie

  486 shared

• Lucas A. Freeman

  178 shared

• Andrew Molino

  Massachusetts Institute of Technology

  163 shared

• Jacob E. Walley

  141 shared

• David J. D. Wilson

  La Trobe University

  141 shared

• Guocang Wang

  102 shared

• Jr. Jr.

  95 shared

• Kelsie E. Wentz

  Johns Hopkins University

  75 shared

Awards & honors

• Novartis Professor of Chemistry