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Donald Darensbourg

Donald Darensbourg

· Distinguished Professor, Fellow of ACS, AMACAD, NASVerified

Texas A&M University · Chemistry

Active 1967–2026

h-index81
Citations27.1k
Papers61442 last 5y
Funding$1.5M
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About

Donald Darensbourg is a Distinguished Professor at Texas A&M University College of Arts and Sciences, with a focus on catalysis, inorganic materials, organometallic chemistry, polymer science, and sustainability research. His research centers on the chemistry associated with carbon dioxide, exploring its potential as a source of chemical carbon and aiming to develop improved synthetic routes for polycarbonates, which are traditionally produced through hazardous and expensive processes. His work involves establishing mechanistic views of bond-forming processes resulting from carbon dioxide insertion into various bonds, and utilizing in situ spectroscopy methods such as FTIR/ATR to study these reactions. Additionally, his research addresses the development of structural and reactivity models for catalysts used in polyether and polycarbonate synthesis from epoxides and CO2, with an emphasis on understanding reaction kinetics and mechanisms to facilitate industrial applications.

Research topics

  • Chemistry
  • Organic chemistry
  • Materials science
  • Polymer chemistry
  • Waste management
  • Physical chemistry
  • Nanotechnology
  • Chemical engineering
  • Composite material
  • Biochemical engineering

Selected publications

  • Role of Stereochemistry in Controlling Magnetic Behavior in Polymeric Materials

    Journal of the American Chemical Society · 2026-05-18

    articleOpen accessSenior author

    ). These magnetic switchable polymers are expected to be suitable for various device applications.

  • Eugenol‐Derived Sustainable Cyclic Carbonates and Polythiocarbonates from CO <sub>2</sub> and COS as Efficient Hybrid Catalysts for Suzuki–Miyaura Cross‐Coupling Reactions

    Advanced Sustainable Systems · 2026-04-01

    articleOpen accessSenior authorCorresponding

    ABSTRACT Currently, the increasing demand for sustainable and degradable polymers from resources that reduce the reliance on petroleum‐based materials is receiving much attention. This transition is driven by the unchecked and persistent accumulation of non‐biodegradable wastes in the ecosystem. Herein, a novel palladium‐ligated polymer catalyst was prepared via the copolymerization of COS and eugenol‐based bio‐epoxide. The property of the copolymer was greatly enhanced by post‐polymerization modification via alkyne‐azide click chemistry, followed by effective incorporation of palladium (Pd) in the polymeric chain. Copolymerization was catalysed by binary catalytic systems comprising (salen)CrX or (salophen)CrX in combination with onium salts to afford poly(monothiocarbonate)s with good yield. The chemical composition and structures of resulting materials were characterized by spectroscopic techniques like FTIR, 1 H NMR and ESI‐MS. The synthesized polymer was subsequently evaluated as a hybrid catalyst for Suzuki cross‐coupling reactions, exhibiting high catalytic efficiency at lower catalyst loadings and excellent recyclability with negligible loss of catalytic activity. A corresponding Pd complex containing a cyclic carbonate ligand was also synthesized to compare its catalytic activity with the polymeric catalyst, which shows comparatively less activity and no recyclability. Hence, this work presents a method for fabricating a highly active bio‐based polymeric catalyst and expanding the scope of green chemistry.

  • Eugenol-Derived Bipyridine Ligand Scaffolds: Design, Metal Coordination, and Catalytic Applications in Cyclic Carbonate Synthesis

    ACS Omega · 2026-02-05

    articleOpen access

    were also evaluated for cyclic carbonate synthesis, which revealed that these metal complexes lacked the catalytic ability for this transformation.

  • CCDC 2502211: Experimental Crystal Structure Determination

    The Cambridge Structural Database · 2026-05-19

    datasetOpen accessSenior author

    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.

  • Bioderived, 3D-Printable, and Biocompatible Polycarbonate/Hydroxyapatite Composite Scaffolds

    ACS Sustainable Chemistry & Engineering · 2025-10-03 · 1 citations

    articleCorresponding

    Regenerative strategies for bone repair would benefit from scaffolds that are mechanically resilient and biologically compatible. We present a fully bioderived and 3D-printable composite scaffold that meets these requirements while offering environmental sustainability through the integration of CO2-derived eugenol polycarbonate, bioderived cross-linkers, and hydroxyapatite (HAp) reinforcement. This scaffold exhibits excellent thermal stability (Tg ≥ 60 °C and Td ≥ 350 °C) and robust mechanical properties (flexural modulus ∼ 2.54 GPa and compressive modulus ∼ 220 MPa), aligning with the mechanical properties of human trabecular bone and outperforming reported polymer/HAp composites. It demonstrates exceptional creep resistance (∼0.82% strain under 3 MPa for 24 h), ensuring long-term mechanical integrity under physiological loads. A UV-assisted direct ink writing (DIW) technique, followed by post-UV curing, fabricates precise 3D structures that support cell attachment. The hydrophilicity of the scaffold is tunable via surface modifications to optimize cell-material interactions. In vitro cytocompatibility studies using MC3T3 preosteoblasts show >91% viability. Under simulated physiological conditions (PBS, 37 °C), the scaffold shows negligible mass loss over 18 weeks. Compared to conventional 3D-printed scaffolds that rely on petrochemical feedstocks and exhibit weaker mechanical resilience, this sustainable system offers a compelling combination of printability, mechanical robustness, and biocompatibility with potential for advanced bone regenerative therapies.

  • Monomer-Dependent Selectivity in Sulfur-Containing Ring-Opening Copolymerisation : Bimetallic Catalysis for Predictive Design of Degradable Polymers

    EPub Bayreuth (University of Bayreuth) · 2025-01-01

    articleOpen access

    Sulfur-containing polymers offer unique opportunities for advanced materials due to their inherent degradability, high refractive indices, and potential for chemical recyclability. Yet, synthetic strategies for their precise construction remain underdeveloped and monomer selection rules to achieve this are elusive. Herein, we achieve the first comprehensive evaluation of sulfurated ring-opening copolymerisations (ROCOP) performed under unified conditions using a single heterobimetallic Cr(III)/Rb(I) catalyst platform. Although such catalysts are largely unexplored in sulfur-based ROCOP, our study demonstrates their remarkable synergistic performance in controlling both activity and selectivity across diverse heteroallene/epoxide systems. We identify carbonyl sulfide (COS) as the most promising monomer, enabling perfectly alternating copolymers under mild conditions on kinetic grounds. As a close second, PhNCS emerges as a viable, easier to handle, alternative that offers selective access to sulfur-containing copolymers. In contrast, thioanhydrides and CS2 show progressively lower selectivity, with increasing O/S scrambling and small molecule byproduct formation. This study provides the first predictive framework linking sulfur monomer identity to selectivity and reactivity under unified conditions, enabling rational design of degradable sulfur-rich polymers.

  • Axial Carbonate-Bridged Dy<sub>2</sub> Complexes Having Rigid N<sub>3</sub>O<sub>2</sub> Equatorial Planes: Stepwise Boosting and Tuning of the Zero-Field SMM Behavior

    Crystal Growth & Design · 2025-03-13 · 4 citations

    articleOpen accessSenior authorCorresponding

    Herein, we report the synthesis of carbonate-bridged binuclear Ln(III) complexes [Dy2(L12–)2(CO32–)(MeOH)2] complex 1-Dy2, [Y2(L12–)2(CO32–)(MeOH)2] complex 1-Y2, [Dy2(L12–)2(CO32-)(MeOH)(TPPO)] complex 2-Dy2, [Y2(L12–)2(CO32–)(MeOH)(TPPO)] complex 2-Y2, [Dy2(L12–)2(CO32–)(TPPO)2] complex 3-Dy2, and [Dy2(H2L22–)2(CO32–)(TPPO)2] complex 4-Dy2, having a rigid equatorial pentagonal plane around each Ln(III) ion. The Schiff base H2L1 (2,6-diacetylpyridine bis-benzoyl hydrazone) and H4L2 (2,6-diacetylpyridine bis-salicyl hydrazone) ligands were used to provide a rigid equatorial pentagonal plane to the Ln(III) ions through their N3O2 donor atoms. One of the axial sites of each Ln(III) is occupied by triphenylphosphine oxide (TPPO) or methanol ligand, while CO32– occupies the other axial sites. The successful replacement of axially coordinated methanol by the TPPO ligand boosted the zero-field SMM property in 3-Dy2. We observed that phenolic −OH in H2L22– ligands imposes significant structure orientation in 4-Dy2 compared to 3-Dy2 and tunes the zero-field SMM properties by altering the Dy1-O-Dy2 bridging angle.

  • 5‐Hydroxymethylfurfural Derived Epoxy Monomers Reactions With COS: Synthesis of Polymeric Thiocarbonates with Pendant Aldehyde or Vinyl Groups

    Macromolecular Rapid Communications · 2025-06-19 · 2 citations

    articleOpen accessSenior authorCorresponding

    ABSTRACT The shift toward eco‐friendly polymers is undeniably exciting and necessary, especially as industries strive to reduce their reliance on petroleum‐based materials. In this communication, we have showcased the synthesis of epoxy monomers derived from biobased platform chemicals, specifically 5‐hydroxymethyl‐2‐furfural (5‐HMF) and epichlorohydrin (ECH), used as starting materials. The study of its coupling reactions with CO 2 and its sulfur congener COS has been evaluated utilizing a well‐defined binary (salen)MX/PPNX catalyst system. It was found that the reactions with CO 2 predominantly produced cyclic products, while the more reactive COS led to the formation of aldehyde functional poly(monothiocarbonate)s (PMTC) in a regioselective manner at ambient temperature. Furthermore, the post‐polymerization reactions of aldehydes with primary amines bearing alkene, alkyne, and radical functional groups led to the production of corresponding imine derivatives, thereby providing a pathway to well‐defined, highly modifiable polymers. This process has the potential to promote a more sustainable approach for transforming a wide array of polymeric materials while introducing desirable features such as (bio)degradability for various applications.

  • Gateway to Sustainable Polymers via Catalytic ROCOP of CO <sub>2</sub> /COS Utilizing a Renewable Epoxide Monomer from Furfural Derivatives

    ACS Sustainable Chemistry & Engineering · 2025-10-08 · 1 citations

    articleOpen accessSenior authorCorresponding

    s of 58.6 and 49.2 °C, respectively. The aliphatic polycarbonate exhibited hydrolytic degradability under basic conditions to produce diol. The diol generated by the degradation of polycarbonate was recycled back to epoxide monomer through tosylation reaction, followed by ring-closing of the tosylated product. The mechanical properties of the polymer sample were accessed by performing a lap shear test and nanoindentation testing. The lap shear test revealed that the polycarbonate sample exhibited better adhesive performance than poly-(monothiocarbonates), while nanoindentation testing showed poly-(monothiocarbonates) exhibited higher hardness and elastic modulus than polycarbonates.

  • Field-induced slow-magnetic relaxation behaviours of Dy(III) ions in Dy2 dimeric complexes

    Polyhedron · 2025-10-23

    articleOpen accessSenior authorCorresponding

    A series of dimeric Dy 2 complexes 1 – 3 was constructed using the 2,6-diacetylpyridine bis-salicyl hydrazone ligand system L N3O2 (provides equatorial N 3 O 2 donor atoms) and linkers derived from hydrazine and vanillin ( L 1 ) or 4-hydroxybenzaldehyde ( L 2 ). These linkers coordinate from one of the axial sites of Dy(III) ions, and the other axial sites can be occupied by water or triphenylphosphine oxide (TPPO). Single crystal X-ray diffraction data reveal the molecular formulae of [Dy 2 (H 2 L N3O2 ) 2 ( L 1 )(H 2 O) 2 ], [Dy 2 (H 2 L N3O2 ) 2 ( L 1 )(TPPO) 2 ], [Dy 2 (H 2 L N3O2 ) 2 ( L 2 )(PPh 3 O) 2 ], respectively, for complexes 1 – 3 . The field-induced slow-magnetic relaxation behavior was observed for all these complexes, with Orbach U eff = 11 cm −1 ( τ 0 = 2.0 × 10 −5 s −1 ), U eff = 12.5 cm −1 ( τ 0 = 7.9 × 10 −6 s −1 ) and U eff = 7.65 cm −1 ( τ 0 = 9 × 10 −5 s −1 ) and dominating Raman magnetic relaxation processes. Ab initio theoretical studies were performed on the optimized X-ray structures of these complexes to rationalize the experimental observations. Graphical abstract Herein, we report the synthesis, crystal structure, and magnetic properties of a series of Dy 2 dimeric complexes 1 – 3 . In these dimeric complexes, Dy(III) ions are coordinated by equatorial N 3 O 2 donor atoms furnished by the doubly deprotonated hydrazone H 2 L N3O2 ligand systems, and the axial sites are either occupied by water or triphenylphosphine oxide. The two Dy(III) ions then connected with doubly deprotonated linkers L 1 and L 2 . The role of linkers is to separate two Dy(III) ions with a suitable distance to avoid intramolecular dipolar interaction. We did not observe zero-field out-of-phase ( χ M ” ) signals in ac magnetic susceptibility measurements for any of these complexes 1 – 3 , but on application of an optimum dc magnetic field, signals appeared. The data fitting and analysis revealed that Raman magnetic relaxations are active in all these reported complexes and are responsible for the low effective energy barrier U eff for spin reversal through the Orbach process. Further, ab initio energy barrier, magnetic anisotropies, and plausible magnetic relaxation mechanism were computed using OpenMolcas. To understand the major types of intermolecular interactions and their effect on the magnetic relaxation, we also computed the Hirshfeld surface analysis using CrystalExplorer software.

Recent grants

Frequent coauthors

  • Joseph H. Reibenspies

    179 shared
  • Marcetta Y. Darensbourg

    104 shared
  • J.C. Yarbrough

    82 shared
  • Gulzar A. Bhat

    University of Kashmir

    46 shared
  • Samuel J. Kyran

    Texas A&M University

    46 shared
  • D.R. Billodeaux

    39 shared
  • Ming Luo

    31 shared
  • Ashfaq A. Bengali

    Texas A&M University at Qatar

    30 shared

Education

  • Ph.D., Chemistry

    University of Illinois at Urbana-Champaign

    1968

Awards & honors

  • SEC Faculty Achievement Award (2023)
  • Michele Aresta Prize in CO2 Utilization Research Award (ICCD…
  • Member, National Academy of Sciences (2022)
  • American Academy of Arts & Sciences Fellow (2019)
  • ACS Inorganic Award for Undergraduate Researcher - Tucker Fo…
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