About

Professor Phillip Milner is an associate professor of Chemical & Chemical Biology at Cornell University. His teaching and research interests lie at the intersection of organic and materials chemistry. His primary research focuses include the development of new methods for organic synthesis and identifying new chemistries for separations, which currently account for 15% of global energy use. His group harnesses the power of framework materials to unlock new possibilities in catalysis and chemical separations, designing heterogeneous reagents and catalysts for the late-stage functionalization of bioactive molecules to open new doors in drug development. The Milner group also develops novel strategies to safely handle gases as solid reagents, with applications in pharmaceutical synthesis and therapeutic delivery. Employing their organic chemistry expertise, the group develops new reactivity-based chemical separations critical to addressing climate change. Additionally, they synthesize new materials for applications in electrochemistry, photocatalysis, and chemical separations, contributing to advancements in sustainable and environmentally relevant chemical processes.

Research topics

• Chemistry
• Materials science
• Crystallography
• Chemical engineering
• Organic chemistry

Selected publications

• Electroreductive Radical Olefin Difunctionalization with Fluorinated Gases Enabled by Dosage Delivery from a Metal-Organic Framework

  ChemRxiv · 2026-01-23

  articleOpen accessSenior author

  Fluoroalkyl groups are crucial for tuning the pharmacokinetic properties of drug-like molecules, motivating the development of practical methods for their late-stage installation. Despite extensive progress, most contemporary fluoroalkylation strategies rely on impractical reagents or harsh reaction conditions, limiting their sustainability and scalability. Electrochemistry offers a compelling alternative by enabling controlled and tunable radical generation under mild conditions; however, electrochemical fluoroalkylation reactions, particularly reductive transformations, remain significantly underdeveloped. Herein, we report a general platform for electroreductive olefin difunctionalization that employs simple fluoroalkyl iodide gases (CF3I, CF3CF2I, CF2HI) handled safely using the robust, inexpensive, recyclable, and redox-innocent metal-organic framework (MOF) Al-fum. Our method delivers streamlined access to fluoroalkylated products and enables the first electroreductive olefin difunctionalization method for installing the medicinally important CF₂H group. All reactions proceed with broad functional group tolerance (including for other alkyl halides) and are suitable for follow-on diversification. Together, our findings expand the scope of electroreductive fluoroalkylation chemistry and establish gas-MOF reagents as powerful tools for electroorganic synthesis.

  PublisherOA PDFDOI

• Organic photochemistry for direct light-driven separations

  Chemical Science · 2026-01-01

  articleOpen access

  and selective anion recovery from water. We highlight key design strategies for photo-pH-swing capture and identify current practical limitations toward translating solar-driven separations into technologies with meaningful impact.

  PublisherOA PDFDOI

• Late-Stage Fluorosulfurylation using Sulfuryl Fluoride Bound within a Metal-Organic Framework

  ChemRxiv · 2026-01-23

  articleOpen accessSenior author

  Organic S(VI) fluorides have garnered substantial interest for covalent drug discovery and chemoproteomics due to their ambient stability and unique electrophilic reactivity. Sulfuryl fluoride (SO 2 F 2 ) is the ideal reagent for the synthesis of various S(VI)–F moieties, yet it is a toxic greenhouse gas, often making it incompatible with laboratory settings. Developing a strategy for handling SO 2 F 2 that is amenable to high-throughput reaction discovery would enhance its utility in the laboratory without necessitating specialized equipment or extensive safety measures. Herein, we report a strategy to safely store reactive SO 2 F 2 within a metal–organic framework (MOF) for its facile application to the synthesis of electrophilic, bioactive molecules. The solid SO 2 F 2 –Mg 2 (dobdc) reagent can be stored for at least five months with minimal gas loss due to the strong yet reversible interaction between SO 2 F 2 and Mg 2+ centers in the MOF, as confirmed by single-crystal X-ray diffraction. Using this reagent, we prepare a range of drug-like arylfluorosulfates, saturated N -heterocyclic sulfamoyl fluorides, and N -heteroarene sulfamoyl fluorides. These findings represent the first experimental study of SO 2 F 2 adsorption within a MOF and the first use of MOFs for late-stage fluorosulfurylation, paving the way towards a general approach to carefully handle dangerous, reactive gases as solid reagents.

  PublisherOA PDFDOI

• Shining a Light on the Photophysics of Tetraaryl[3]cumulene-Based Metal–Organic Frameworks

  ACS Materials Letters · 2026-03-11

  articleSenior authorCorresponding

  Achieving bright and long-lived emission with π-conjugated organic chromophores in the solid state presents a significant challenge but also an opportunity for applications ranging from nanoscale electronics to heterogeneous photocatalysis. Tetraaryl[n]cumulenes, organic molecules consisting of three or more cumulative double bonds, are highly modular systems with tunable redox and optoelectronic properties, yet their utility remains limited due to rapid quenching from aryl group planarization or excimer formation. Herein, we demonstrate that the incorporation of a tetraaryl[3]cumulene-based organic linker within a metal–organic framework (MOF) suppresses these quenching pathways. Extensive transient absorption (TA) and photoluminescence (PL) spectroscopic studies support the unique properties of the MOF and also confirm it exhibits spectral diffusion, leading to red-shifted steady-state emission compared to molecular analogues in solution. Overall, our findings represent a new avenue to unlock the promising photochemical properties of cumulenes within materials platforms, paving the way for their use in various applications.

  PublisherDOI

• Caging the Chlorine Radical: Chemoselective Photocatalytic C(sp ³ )–H Functionalization Enabled by Terminal Cu–Cl Sites in a Metal–Organic Framework

  Journal of the American Chemical Society · 2026-01-02 · 2 citations

  articleOpen accessSenior authorCorresponding

  Hydrogen atom transfer (HAT) mediated by halogen radicals represents a powerful approach for the functionalization of inert C(sp3)–H bonds. Chlorine radical (Cl•), for example, is capable of generating carbon-centered radicals by abstracting strong C–H bonds (H–Cl bond dissociation energy = 103 kcal/mol). However, the chemoselectivity of these transformations typically suffers due to the high reactivity of Cl•. Herein, we disclose a novel strategy employing a metal–organic framework (MOF) to tame Cl• and effect the selective alkylation of C(sp3)–H bonds. Under light irradiation, MIT20-LiCl─an anionic Cu(II) MOF containing terminal Cu–Cl sites─undergoes ligand-to-metal charge transfer (LMCT) to generate a Cl•-like species that acts as an HAT mediator. MIT20-LiCl is a superior C(sp3)–H alkylation catalyst compared to soluble CuCl2 and allows for the chemoselective alkylation of alcohols without overoxidation. We further demonstrate that this protocol can be used to facilitate C(sp3)–H alkylation of ethers, amines, alcohols, and benzylic sites with broad functional group tolerance. Mechanistic experiments and density functional theory (DFT) calculations support that the framework effectively attenuates the reactivity of Cl• generated within its pores. Further, the heterogeneous MOF catalyst can be easily recycled and used in consecutive reactions without a loss in yield, making it a promising platform for sustainable C(sp3)–H functionalization.

  PublisherOA PDFDOI

• Author response for "Organic Photochemistry for Directly Light-Driven Separations"

  2026-03-17

  peer-review
  PublisherDOI

• Interrogating the Carboxylation of Potassium β-Diketonates and β-Diketiminates by Carbon Dioxide

  The Journal of Organic Chemistry · 2026-02-18

  articleSenior authorCorresponding

  Enolate carboxylation by CO2 is essential to applications ranging from polymer synthesis to CO2 capture, yet the CO2 reactivity of stabilized enolates, such as β-dicarbonyl enolates, remains understudied. Combining detailed NMR and DFT studies, we report the reactivity of diverse potassium β-diketonates and β-diketiminates toward CO2. Our findings reveal the critical role of β′-substituents on β-diketiminates and an unexpected CO2-concentration-dependent reactivity switch, offering structural insights for designing materials with tunable CO2 reactivity.

  PublisherDOI

• CCDC 2527617: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2026-03-16

  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.

  PublisherDOI

• Shining a Light on the Photochemistry of Tetraaryl[3]cumulene-Based Metal-Organic Frameworks

  ChemRxiv · 2026-02-04

  articleOpen accessSenior author

  Achieving bright and long-lived emission with π-conjugated organic chromophores in the solid state presents a significant challenge but also an opportunity for applications ranging from nanoscale electronics to heterogeneous photocatalysis. Tetraryl[n]cumulenes, organic molecules consisting of three or more cumulative double bonds, are highly modular systems with tunable redox and optoelectronic properties, yet their utility remains limited due to rapid quenching from aryl group planarization or excimer formation. Herein, we demonstrate that the incorporation of a tetraryl[3]cumulene-based organic linker within the metal-organic framework (MOF) CORN-MOF-9 (CORN = Cornell University) suppresses these quenching pathways, allowing for bright and long-lived emission. Extensive transient absorption (TA) and photoluminescence (PL) spectroscopic studies support the unique properties of the MOF and also confirm it exhibits spectral diffusion, leading to red-shifted steady-state emission compared to molecular analogs in solution. Overall, our findings represent a new avenue to unlock the promising photochemical properties of cumulenes within materials platforms, paving the way for their use in various applications. Introduction.

  PublisherDOI

• Electroreductive Radical Olefin Difunctionalization with Fluorinated Gases Enabled by Dosage Delivery from a Metal–Organic Framework

  Journal of the American Chemical Society · 2026-04-22

  articleOpen accessSenior authorCorresponding

  Fluoroalkyl groups are crucial for tuning the pharmacokinetic properties of drug-like molecules, motivating the development of practical methods for their late-stage installation. Despite extensive progress, most contemporary fluoroalkylation strategies rely on impractical reagents or harsh reaction conditions, limiting their sustainability and scalability. Electrochemistry offers a compelling alternative by enabling controlled and tunable radical generation under mild conditions; however, electrochemical fluoroalkylation reactions, particularly reductive transformations, remain significantly underdeveloped. Herein, we report a general platform for electroreductive olefin difunctionalization that employs simple fluoroalkyl iodide gases (CF3I, CF3CF2I, and CF2HI) handled safely using the robust, inexpensive, recyclable, and redox-innocent metal–organic framework (MOF) Al–fum. Our method delivers streamlined access to fluoroalkylated products and enables electroreductive olefin difunctionalization for installing the medicinally important CF2H group. All reactions proceed with broad functional group tolerance (including for other alkyl halides) and are suitable for follow-on diversification. Together, our findings expand the scope of electroreductive fluoroalkylation chemistry and establish gas–MOF reagents as powerful tools to deliver fluoroalkyl iodide gases for electroorganic synthesis.

  PublisherDOI

Recent grants

• Renewal of "Taming Fluorine: Metal-Organic Frameworks for the Heterogeneous Delivery of Fluorinated Building Blocks"

  NIH · $2.5M · 2020–2030

• CAREER: Unlocking Reactivity-Based Separations of Olefins using Metal-Organic Frameworks

  NSF · $550k · 2021–2026

• Using Metal-Organic Frameworks to Separate Aryl Fluorides from Arenes

  NIH · $107k · 2016–2018

Frequent coauthors

• Jeffrey R. Long

  University of California, Berkeley

  99 shared

• Rebecca L. Siegelman

  University of California, Berkeley

  90 shared

• Alexander C. Forse

  University of Cambridge

  60 shared

• Jung‐Hoon Lee

  Korea Institute of Science and Technology

  53 shared

• Jeffrey D. Martell

  University of Wisconsin Carbone Cancer Center

  52 shared

• Jeffrey A. Reimer

  University of California, Berkeley

  45 shared

• Miguel I. Gonzalez

  Harvard University

  43 shared

• Stephen L. Buchwald

  Massachusetts Institute of Technology

  38 shared

Labs

• Milner GroupPI