# US 8,541,240 B2 · Colorimetric and fluorimetric fluoride sensing

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- Number: US 8,541,240 B2
- Document ID: US8541240B2
- Status: Granted
- Kind: B2
- Application number: 13/149,398
- Filed: 2011-05-31
- Published: 2011-12-01
- Granted: 2013-09-24
- Earliest claimed: 2010-05-28
- Assignees: The Florida State University Research Foundation, Inc.
- Applicants: Sourav Saha; Samit Guha
- Inventors: Sourav Saha; Samit Guha
- Web page: https://patentgrep.com/patent/US8541240B2

## CPC

- C07D 471/06: Peri-condensed systems
- Y10T 436/145555: Hetero-N
- Y10T 436/19: Halogen containing
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The present invention generally relates to fluoride receptor reagent compounds that are derived from one or more N-aryl or heteroaryl substituted 1,4,5,8-naphthalenetetracarboxydiimide (NDI) units. The invention also relates to associated methods for the detection of fluoride in a composition. π-electron orbitals present in the NDI unit of the reagents form a complex with fluoride anions. It is believed that the anion-π interaction results in a charge transfer process between the fluoride anion and the NDI unit, resulting in a number of measurable effects (e.g., colorimetric response).

## Claims

### Claim 1

A method for detecting fluoride anion (F−) in a material comprising:
contacting the material with a fluoride receptor reagent to form a complex involving anion-π interactions, wherein the fluoride receptor reagent comprises an N-aryl or heteroaryl derivative of 1,4,5,8-naphthalenediimide (NDI) having the formula (I):
wherein R1 comprises a substituted or unsubstituted aryl or heteroaryl moiety; and R2 is independently a substituted or unsubstituted aryl or heteroaryl moiety, or R2 comprises a second NDI moiety comprising a second NDI unit and having the formula:
wherein R3 is a linking group connecting the second NDI unit to the nitrogen atom of formula (I) and comprising a substituted or unsubstituted aryl or heteroaryl moiety; and R4 is independently a substituted or unsubstituted aryl or heteroaryl moiety, and
detecting the presence of fluoride anions as indicated by a colorimetric or fluorometric response.

### Claim 2 (depends on 1)

The method of claim 1 wherein the fluoride receptor reagent has the formula (II):
wherein R1 and R4 are each independently a substituted or unsubstituted aryl or heteroaryl moiety; and R3 is a linking group comprising a substituted or unsubstituted aryl or heteroaryl moiety.

### Claim 3 (depends on 2)

The method of claim 2 wherein the R3 linking group comprises a pyridyl moiety.

### Claim 4 (depends on 3)

The method of claim 3 wherein the fluoride receptor reagent has the formula (III):
wherein R5 and R6 are intermediate linking groups, each intermediate linking group independently comprising a substituted or unsubstituted aryl or heteroaryl moiety.

### Claim 5 (depends on 4)

The method of claim 4 wherein R5 and R6 each comprise an amide functional group bonded to the central pyridyl moiety.

### Claim 6 (depends on 1)

The method of claim 1 wherein one or more of R1, R2, R3 and R4 are substituted aryl or heteroaryl-comprising moieties.

### Claim 7 (depends on 6)

The method of claim 6 wherein the substituents on the one or more substituted aryl or heteroaryl-comprising moieties R1, R2, R3 and R4 are independently selected from the group consisting of halo, —OH, ═O, —C(O)OH, —C(O)OR7, —C(O)NR8R9, —CH2NR8R9, nitro (—NO3), sulfonate (—SO3−) hydrocarbyl and substituted hydrocarbyl, wherein R7, R8, and R9 are each independently hydrocarbyl or substituted hydrocarbyl.

### Claim 8 (depends on 7)

The method of claim 7 wherein the hydrocarbyl and substituted hydrocarbyl substituents are independently selected from the group consisting of alkyl, alkylene, alkoxy, alkylamino, thioalkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, aryl, aralkyl heteroaryl, N-heteroaryl and heteroarylalkyl.

### Claim 9 (depends on 1)

The method of claim 1 wherein the fluoride receptor reagent is selected from the group consisting of:
a compound of formula (I-A):
a compound of formula (I-B):
wherein R11 and R12 are each independently alkyl, alkyl ether, or nitro;
a compound of formula (I-C):
wherein X11, X12, X13, and X14 are each independently halo;
a compound of formula (I-D):
wherein X11, X12, X13, and X14 are each independently halo, and R11 and R12 are each independently alkyl, alkyl ether, or nitro;
a compound of formula (I-E):
wherein R13, R14, R15, and R16 are each independently alkyl or alkyl ether;
and a compound of the formula (N1):

### Claim 10 (depends on 1)

The method of claim 1 wherein the material is dissolved in a solvent prior to contacting the fluoride receptor reagent.

### Claim 11 (depends on 10)

The method of claim 10 wherein the solvent is a polar aprotic solvents selected from the group consisting of dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetonitrile, acetone, and tetrahydrofuran.

### Claim 12 (depends on 11)

The method of claim 11 wherein the polar aprotic solvent is dry.

### Claim 13 (depends on 1)

The method of claim 1 wherein the fluoride receptor reagent is selected from the group consisting of:
a compound of formula (III-A):
a compound of formula (III-B):
wherein R21 and R22 are each independently alkyl, alkyl ether, or nitro;
a compound of formula (III-C):
wherein X21, X22, X23, and X24 are each independently halo;
a compound of formula (III-D):
wherein X21, X22, X23, and X24 are each independently halo, and R21 and R22 are each independently alkyl, alkyl ether, or nitro;
a compound of formula (III-E):
wherein R23, R24, R25, and R26 are each independently alkyl or alkyl ether;
a compound of formula (III-F):
a compound of formula (III-G):
wherein R31 and R32 are each independently alkyl, alkyl ether, or nitro;
a compound of formula (III-H):
wherein X31, X32, X33, and X34 are each independently halo;
a compound of formula (III-J):
wherein X31, X32, X33, and X34 are each independently halo, and R31 and R32 are each independently alkyl, alkyl ether, or nitro;
a compound of formula (III-K):
wherein R33, R34, R35, and R36 are each independently alkyl or alkyl ether;
a compound having the formula (SR):
and a compound having the formula (LR):