Partner site with Johnson lab

Many anions are problematic environmental contaminants and are vital to many processes in nature, with anion binding proteins and transport channels implicated in the mechanisms of many disease pathways. This avenue of research is a productive collaboration between the Haley lab and that of UO colleague Darren Johnson to target new organic receptors that selectively bind and sense anions. The project is a union of the synthetic expertise of the Haley group toward the assembly of relatively rigid and inherently fluorescent molecules based on arylethynyl scaffolding with the extensive knowledge of the Johnson lab to design and exhaustively analyze complex supramolecular systems.

The modularity of our design strategy allows for exploration of a variety of recognition motifs for anions, including electrostatic attractions, hydrogen bond interactions and attractions with electron-deficient arenes (anion-π, CH•••X hydrogen bonds and weak-sigma complexes). This flexibility affords the possibility of selectively binding anions that are challenging to target with traditional approaches. Core and linker substitution provides another approach to tuning the selectivity of the receptors by changing the shape and size of the binding pocket, in addition to modification of the fluorescent behavior through adjustment of the electronics of the conjugated core fluorophore. The functionality of the receptors can also be adjusted to provide water-solubility to the molecules or even cell membrane permeability. These sensors will have long-term applications in sensing, imaging and/or remediating anions, which will impact public health in both discovering and removing environmental contaminants and imaging the role anions play in biological processes.

Work on the bis(arylethynyl) bisurea based receptor class led to a successful start-up company, SupraSensor Technologies. Co-founded by Haley, Johnson, and former graduate student Dr. Calden Carroll, SupraSensor targets nitrate detection for applications in precision agriculture. Both the basic research from the Haley/Johnson collaboration as well as the applied science from Carroll and his team were highlighted in an NSF-sponsored “Science Nation” video (http://www.nsf.gov/news/special_reports/science_nation/suprasensor.jsp). SupraSensor was acquired in 2016 by The Climate Corporation.

Relevant Publications

A highly fluorescent PN-heterocycle-fused pyrene derivative with strong self-dimerisation through hydrogen bonding

Bard, J. P.; Mancuso, J. L.; Deng, C.-L.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Supramol. Chem. 2019, In Press.
DOI: 10.1080/10610278.2019.1687896

Amplification of the Quantum Yields of 2-λ5-Phosphaquinolin-2-ones through Phosphorus Center Modification

Bard, J. P.; Bates, H. J.; Deng, C.-L.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. J. Org. Chem. 2019, In Press.
DOI: 10.1021/acs.joc.9b02132

PN-Containing Pyrene Derivatives: Synthesis, Structure, and Photophysical Properties

Deng, C.-L.; Bard, J. P.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Org. Lett. 2019, 21, 6427-6431.
DOI: 10.1021/acs.orglett.9b02332

Naphtho[2,1-e]-1,2-azaphosphorine-2-oxide Derivatives: Synthesis, Optoelectronic Properties, and Self-Dimerization Phenomena

Deng, C.-L.; Bard, J. P.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. J. Org. Chem. 2019, 84, 8131-8139.
DOI: 10.1021/acs.joc.9b00994

The road to aryl CH—anion binding was paved with good intentions: fundamental studies, host design, and historical perspectives in CH hydrogen bonding

Eytel, L. M.; Fargher, H. A.; Haley, M. M.; Johnson, D. W. Chem. Commun. 2019, 55, 5195-5206.
DOI: 10.1039/C9CC01460H

Synthesis, photophysical properties, and self-dimerization studies of 2-λ5-phosphaquinolin-2-ones

Bard, J. P.; Deng, C. L.; Richardson, H. C.; Odulio, J. M.; Barker, J. E.; Zakharov, L. N.; Cheong, P. H.-Y.; Johnson, D. W.; Haley, M. M. Org. Chem. Front. 2019, 6, 1257-1265.
DOI: 10.1039/C9QO00199A

Exploiting the Hydrogen Bond Donor/Acceptor Properties of PN-Heterocycles: Selective Anion Receptors for Hydrogen Sulfate

Deng, C.-L.; Bard, J. P.; Lohrman, J. A.; Barker, J. E.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Angew. Chem. 2019, 131, 3974-3978.; Angew. Chem. Int. Ed. 2019, 58, 3934-3938.
DOI: 10.1002/anie.201814431

Methanesulfonyl-Polarized Halogen Bonding Enables Strong Halide Recognition in an Arylethynyl Anion Receptor

Graphical abstract: Methanesulfonyl-polarized halogen bonding enables strong halide recognition in an arylethynyl anion receptor

Lohrman, J. A.; Deng, C.-L.; Shear, T. A.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W. Chem. Commun. 2019, 55, 1919-1922.
DOI: 10.1039/C8CC09251F

Expanding reversible chalcogenide binding: supremolecular receptors for the hydroselenide (HSe-) anion

Fargher, H. A.; Lau, N.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W.; Pluth, M. D. Chem. Sci. 2019, 10, 67-72.
DOI: 10.1039/C8SC03968B

Conformationally flexible arylethynyl bis-urea receptors bind disparate oxoanions with similar, high affinities

Eytel, L. M.; Brueckner, A. C; Lohrman, J. A.; Haley, M. M.; Cheong, P. H.-Y.; Johnson, D. W. Chem. Commun. 2018, 54, 13208-13211.
DOI: 10.1039/C8CC07301E

Synthesis and Properties of Naphtho[2,3-e]-1,2-azaphosphorine 2-Oxides: PN-Anthracene Analogues

Takaesu, N. A.; Ohta, E.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Organometallics 2017, 36, 2491-2493.
DOI: 10.1021/acs.organomet.7b00281

Computational and Experimental Evidence of Emergent Equilibrium Isotope Effects in Anion Receptor Complexes

Tresca, B. W.; Brueckner, A.C.; Haley, M. M.; Cheong, P. H.-Y.; Johnson, D. W. J. Am. Chem. Soc. 2017, 139, 3962-3965.
DOI: 10.1021/jacs.7b00612

Do CH-Anion and Anion-π Interactions Alter the Mechanism of 2:1 Host-Guest Complexation in Arylethynyl Monourea Anion Receptors?

Eytel, L. M.; Gilbert, A. K.; Gorner, P.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Chem. Eur. J. 2017, 23, 4051-4054.
DOI: 10.1002/chem.201605452

A Synthetic Supramolecular Receptor for the Hydrosulfide Anion”

Hartle, M. D.; Hansen, R. J.; Tresca, B. W.; Prakel, S. S.; Zakharov, L. N.; Haley, M. M.; Pluth, M. D.; Johnson, D. W. Angew. Chem. Int. Ed. 2016, 55, 11480-11484.
DOI: 10.1002/anie.201605757

Harnessing solid-state packing for selective detection of chloride in a macrocyclic anionophore

Vonnegut, C. L.; Shonkwiler, A. M.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W. Chem. Commun. 2016, 52, 9506-9509.
DOI: 10.1039/C6CC03795J

Anion-directed self-assembly of a 2,6-bis(2-anilinoethynyl)pyridine bis(amide) scaffold

Tresca, B. W.; Berryman, O. B.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Supramol. Chem. 2016, 28, 37-44.
DOI: 10.1080/10610278.2015.1072199

Substituent Effects in CH Hydrogen Bond Interactions: Linear Free Energy Relationships and Influence of Anions

Tresca, B. W.; Hansen, R. J.; Chau, C. V.; Hay, B. P.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W. J. Am. Chem. Soc. 2015, 137, 14959-14967.
DOI: 10.1021/jacs.5b08767

Facile Synthesis and Properties of 2-λ5-Phosphaquinolines and 2-λ5-Phosphaquinolinones

Vonnegut, C. L.; Shonkwiler, A. M.; Khalifa, M. K.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Angew. Chem. Int. Ed. 2015, 54, 13318-13322.
DOI: 10.1002/anie.201507696

‘Off-On’ Aggregation-Based Fluorescent Sensor for the Detection of Chloride in Water

Watt, M. M.; Engle, J. M.; Fairley, K. C.; Robitshek, T. E.; Haley, M. M.; Johnson, D. W. Org. Biomol. Chem. 2015, 13, 4266-4270.
DOI: 10.1039/C4OB02409E

Solid-State Examination of Conformationally Diverse Sulfonamide Receptors Based on Bis(2-anilinoethynyl)pyridine, -Bipyridine, and -Thiophene

Berryman, O. B.; Johnson, C. A.; Vonnegut, C. L.; Fajardo, K. A.; Zakharov, L. N.; Johnson, D. W.; Haley, M. M. Cryst. Growth Des. 2015, 15, 1502-1511.
DOI: 10.1021/cg5018856

Ion and Molecular Recognition Using Aryl–Ethynyl Scaffolding

Vonnegut, C. L.; Tresca, B. W.; Johnson, D. W.; Haley, M. M. Chem. Asian J. 2015, 10, 522-535.
DOI: 10.1002/asia.201403212
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Exploring anion-induced conformational flexibility and molecular switching in a series of heteroaryl-urea receptors

Gavette, J. V.; Evoniuk, C. J.; Zakharov, L. N.; Carnes, M. E.; Haley, M. M.; Johnson, D. W. Chem. Sci. 2014, 5, 2899–2905.
DOI: 10.1039/C4SC00950A

Intramolecular N–H•••Cl hydrogen bonds in the outer coordination sphere of a bipyridyl bisurea-based ligand stabilize a tetrahedral FeLCl2 complex

Gavette, J. V.; Klug, C. M.; Zakharov, L. N.; Shores, M. P.; Haley, M. M.; Johnson, D. W. Chem. Commun. 2014, 50, 7173–7175.
DOI: 10.1039/C4CC02297A

Synthesis and solid-state structures of a macrocyclic receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold

J. M. Engle, P. S. Singh, C. L. Vonnegut, L. N. Zakharov, D. W. Johnson and M. M. Haley CrystEngComm 2014, 16, 3703-3706.
DOI: 10.1039/C3CE42307G

Selective Nitrate Binding in Competitive Hydrogen Bonding Solvents: Do Anion–π Interactions Facilitate Nitrate Selectivity?

Watt, M. M.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W. Angew. Chem. Int. Ed. 2013, 52, 10275–10280.
DOI: 10.1002/anie.201303881

An Anion-Modulated Three-Way Supramolecular Switch that Selectively Binds Dihydrogen Phosphate, H2PO4

Gavette, J. V.; Mills, N. S.; Zakharov, L. N.; Johnson, C. A.; Johnson, D. W.; Haley, M. M. Angew. Chem. Int. Ed 2013, 52, 10460–10464.
DOI: 10.1002/anie.201302929

Aryl C–H•••Cl hydrogen bonding in a fluorescent anion sensor

Tresca, B. W.; Zakharov, L. N.; Carroll, C. N.; Johnson, D. W.; Haley, M. M. Chem. Commun. 2013, 49, 7240-7242.
DOI: 10.1039/C3CC44574G

Lithium-selective phosphine oxide-based ditopic receptors show enhanced halide binding upon alkali metal ion coordination

Gavette, J. V.; Lara, J.; Reling, L. L.; Haley, M. M.; Johnson, D. W. Chem. Sci. 2013, 4, 585-590.
DOI: 10.1039/C2SC21501B

Synthesis and optoelectronic properties of 2,6-bis(2-anilinoethynyl)pyridine scaffolds

Engle, J. M.; Carroll, C. N.; Johnson, D. W.; Haley, M. M. Chem. Sci. 2012, 3, 1105-1110.
DOI: 10.1039/C2SC00975G

Molecular Self-Assembly: Solvent Guests Tune the Conformation of a series of 2,6-Bis(2-anilinoethynyl)pyridine-Based Ureas

Engle, J. M.; Lakshminarayanan, P. S.; Carroll, C. N.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W. Cryst. Growth Des. 2011, 11, 5144-5152.
DOI: 10.1021/cg201074v

Lithium cation enhances anion binding in a tripodal phosphine oxide-based ditopic receptor

Gavette, J. V.; Lara, J.; Berryman, O. B.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W. Chem. Commun. 2011, 47, 7653-7655.
DOI: 10.1039/C1CC12475G

Anion-dependent fluorescence in bis(anilinoethynyl)pyridine derivatives: switchable ON–OFF and OFF–ON responses

Carroll, C. N.; Coombs, B. A.; McClintock, S. P.; Johnson II, C. A.; Berryman, O. B.; Johnson, D. W.; Haley, M. M. Chem. Commun. 2011, 47, 5539-5541.
DOI: 10.1039/C1CC10947B

Arylethynyl receptors for neutral molecules and anions: emerging applications in cellular imaging

Carroll, C. N.; Naleway, J. J.; Haley, M. M.; Johnson, D. W. Chem. Soc. Rev. 2010, 39, 3875–3888.
DOI: 10.1039/B926231H

Anion Binding Induces Helicity in a Hydrogen-Bonding Receptor: Crystal Structure of a 2,6-Bis(anilinoethynyl)pyridinium Chloride

Johnson, C. A.; Berryman, O. B.; Sather, A. C.; Zakharov, L. N.; Haley, M. M.; Johnson , D. W. Cryst. Growth Des., 2009, 9, 4247–4249.
DOI: 10.1021/cg900674p

Protonation activates anion binding and alters binding selectivity in new inherently fluorescent 2,6-bis(2-anilinoethynyl)pyridine bisureas

Carroll, C. N.; Berryman, O. B.; Johnson, C. A.; Zakharov, L. N.; Haley, M. M.; Johnson, D. W. Chem. Commun. 2009, 18, 2520–2522.
DOI: 10.1039/B901643K

Water and Hydrogen Halides Serve the Same Structural Role in a Series of 2+2 Hydrogen-Bonded Dimers Based on 2,6-Bis(2-anilinoethynyl)pyridine Sulfonamide Receptors


Berryman, O. B.; Johnson, C. A.; Zakharov, L. N.; Haley, M. M.; Johnson D. W. Angew. Chem. Int. Ed. 2008, 47, 117-120.
DOI: 10.1002/anie.200703971