Fluorescent halogen bonding arylethynyl scaffolds for anion recognition
Inventors
Lohrman, Jessica • Johnson, Darren W. • Haley, Michael M. • Berryman, Orion B. • Riel, Asia M. • Decato, Daniel A.
Assignees
University of Oregon • University of Montana Missoula
Publication Number
US-11021447-B2
Publication Date
2021-06-01
Expiration Date
2039-05-01
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Abstract
A compound, or a protonate or salt thereof, of formula I:wherein Y is aryl, substituted aryl, heteroaryl, or substituted heteroaryl;n is 1 or 2;each R10 is independently alkyl, substituted alkyl, a polyether moiety, carboxyl, substituted carboxyl, alkoxy, substituted alkoxy, haloalkyl, halogen, nitro, amino, aryloxy, aryl, substituted aryl, cyano, hydroxyl, carbonylamino, aminocarbonyl, acyl, sulfonyl, or substituted sulfonyl;a is 0 to 4; is an aryl or heteroaryl ring; and each R is independently halogen, carbonylamino, sulfonamide, carboxylic acid or hydrogen, provided at least one R is a halogen; andprovided that if Y is are not respectively.
Core Innovation
The invention provides compounds, or protonates or salts thereof, comprising arylethynyl scaffolds with halogen bonding capabilities for anion recognition. These compounds utilize neutral para-positioned electron withdrawing groups that can polarize halogen bond donating groups within the arylethynyl structure. The design enables the receptor compounds to reversibly bind anions in solution and to demonstrate a spectroscopic response, such as a shift in fluorescence, upon binding.
The invention addresses the general problem of the lack of ligand-specific host molecules, particularly for binding toxic ions and small molecules, as well as the scarcity of host compounds capable of reporting binding events through observable spectral shifts. Anion detection is especially challenging because anions are typically large, have low charge-to-radius ratios, possess high solvation enthalpies, and exhibit pH sensitivity and a wide range of geometries.
The disclosed compounds also utilize a novel intramolecular hydrogen bonded-halogen bond (HB-XB) strategy to preorganize halogen bonding molecules and enhance halogen bond interactions. The HB-XB approach simultaneously preorganizes the receptor for binding and increases the electrophilicity of halogen bond donors, resulting in improved anion binding in competitive polar solvents. These features allow for solution-phase halogen-bond-mediated processes for selective anion detection, extraction, or transport in chemical, biological, medical, and environmental contexts.
Claims Coverage
There are several independent claims in the patent, each outlining key inventive features related to halogen bonding arylethynyl compounds, receptor-ligand complexes, and detection methods.
Arylethynyl halogen bonding compound of formula I
A compound, or a protonate or salt thereof, of formula I, where: - Y is aryl, substituted aryl, heteroaryl, or substituted heteroaryl - n is 1 or 2 - Each R10 is independently selected from alkyl, substituted alkyl, a polyether moiety, carboxyl, substituted carboxyl, alkoxy, substituted alkoxy, haloalkyl, halogen, nitro, amino, aryloxy, aryl, substituted aryl, cyano, hydroxyl, carbonylamino, aminocarbonyl, acyl, sulfonyl, or substituted sulfonyl - a is 0 to 4 - The core aromatic or heteroaromatic ring is present - Each R is independently halogen, carbonylamino, sulfonamide, carboxylic acid, or hydrogen, with at least one R being a halogen - Specific structural exclusions as detailed in the claim This structure defines the core of the halogen bonding arylethynyl scaffold for anion recognition.
Receptor-ligand structure comprising the compound
A receptor-ligand structure in which the disclosed compound of formula I (as defined above) serves as a receptor, and the ligand may include at least one anion selected from Cl−, Br−, I−, H2PO4−, HSO4−, ClO4−, NO3−, PF6−, TsO−, OTf−, BArF−, BF4−, HS−, SbF6−, ReO4−, TcO4−, or SCN−. This coverage includes the use of the compounds as selective anion receptors.
Method for detecting an anion using the compound
A method for detecting for the presence of an anion in a system, comprising: - Contacting a sample from the system with a compound, or a protonate or salt thereof, as defined in the core formula This feature protects the method of using the compound for anion detection.
Arylethynyl halogen bonding compound of alternative formula
A compound, or a protonate or salt thereof, of formula I with alternative or additional chemical features as described in claims 19–27, including: - Variant substituent patterns (e.g., a is 0, at least one R is —I, both R groups are —I, Z is —NH2, —Br, or —I) - The same general structural theme with variable details to broaden the chemical space covered by the claim This inventive feature ensures coverage for other substituted scaffolds described in the patent.
The inventive features of the patent claim novel halogen bonding arylethynyl compounds with specific substitution patterns and chemical structures, their use as receptors in complex with anions, and methods for detecting anions using these compounds.
Stated Advantages
The compounds provide reversible and selective binding of anions with a detectable spectroscopic response upon binding, such as fluorescence shifts.
The HB-XB preorganization enhances halogen bond interaction and receptor preorganization, leading to improved anion binding affinity, particularly in competitive polar solvents.
The invention overcomes the intrinsic challenges associated with designing selective host systems for anions, including low charge-to-radius ratios and poorly defined coordination preferences.
The compounds and methods enable selective detection, extraction, or transport of negatively charged species in chemical, biological, medical, and environmental processes.
Documented Applications
Detection of anions in solution by observing a spectroscopic response (e.g., fluorescence shift) upon binding.
Selective detection, extraction, or transport of anions for chemical, biological, medical, and environmental applications.
Use of receptor compounds within membranes of electronic devices, such as field effect transistors, ion-selective electrodes, microfluidics, electrochemical cells, pre-concentration membranes, or lab-on-a-chip devices, to provide electrical readout of anion detection.
Application as colorimetric sensors undergoing a color change or gelation in the presence of specific anions, such as halides and perchlorate.
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