Materials coated with calixarenes

1. A material grafted on its surface with an ultra-thin layer of one or more substituted (thia)calix[n]aryls, as represented below

wherein

n is the number of aryl moieties forming the (thia)calix[n]aryl ring being 4, 5, or 6; X represents CH 2 , S, SO or SO 2 ;

a carbon of one arene ring of the (thia)calix[n]aryls being covalently and directly anchored to the material's surface;

R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent hydrogen or C 1-30 alkyl optionally substituted with one or more substituents each independently selected from the group consisting of halo, carboxylic acid ester, alkyl or benzyl thioester, alkenyl, alkynyl, C 1-30 alkoxy, aryl, substituted aryl (wherein the substituent is fluoro or cyano or C 1-30 alkyl or C 1-30 alkoxy), —N 3 , cyano, carboxylic acid, carboxylic acid amide, —OH, amino, amido, imino, carbamate, acyl chloride, ureido, thioureido, mercapto, substituted disulfide, heterocyclic, amino acid and amino acid derivative, peptide, phosphine or phosphine oxide, crown ether, aza-crown ether, cryptand, porphyrin, calixarene, cyclodextin, resorcinarene, saccharide, and polyethylene glycol; and wherein two or more of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be covalently linked either directly or by a bridge that includes oxygen, phosphine, phosphine oxide, sulfur, SO, SO 2 , amino, imino, amido, ureido, thioureido, ester, thioester, alkene, alkyne or alkyl;

Y 1 —, Y 2 —, Y 3 —, Y 4 — and Y 5 — each independently represent a covalent link with the material's surface, or Y 1 —, Y 2 —, Y 3 —, Y 4 — and Y 5 — are each independently selected from the group consisting of OH, hydrogen, NO 2 , halogen, N 2 + A − , wherein A − is an anion, C 1-30 alkyl, carboxylic acid and derivatives thereof, acyl, —N 3 , alkenyl, and alkynyl.

2. The material according to claim 1 , wherein the ultra-thin layer grafted on the surface of the material is a monolayer.

3. The material according to claim 1 , wherein the material is a conductor, semiconductor, insulator, a composite material, a nanoparticle, a polymer, or a nanotube.

4. The material according to claim 1 , wherein X is methylene and the indexes 0,1 at the right sides of the aryl moieties bearing R 5 and R 6 are both 0.

5. The material according to claim 1 , wherein R 2 , R 3 , and R 4 and, if present, R 5 and R 6 have the same meaning while R 1 has a different meaning; or wherein all of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , have the same meaning.

6. The material according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , are each independently a hydrogen or an optionally substituted C 1 -C 30 alkyl.

7. The material according to claim 1 , wherein of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are n-propyl, —CH 2 —COOH, —CH 2 —COOC 1 -C 4 alkyl, or —(CH 2 ) 3 —CF 3 .

8. The material according to claim 1 , wherein all of Y 1 , Y 2 , Y 3 , and if present, Y 4 and Y 5 are the same.

9. The material according to claim 1 , wherein the immobilized (thia)calix[n]arenes are post-functionalized through the anchoring of chemical species selected from molecules, nanoparticles, biomolecules, ligands for metal ions or anions, molecular receptors, oligomers and polymers.

10. The material according to claim 1 , wherein the ultra-thin layer has a thickness from 1 nm to 4 nm.

11. The material according to claim 10 , wherein n is 4.

12. The material according to claim 10 , being selected from the group consisting of metals, metal alloys, metal compounds, metal oxides, nanoparticles, carbon, glass beads, silica, and silicon wafers.

13. The material according to claim 12 , wherein said metal or metal oxide is selected from the group consisting of gold, silver, nickel, iron oxide, and titanium oxide.

14. The material according to claim 12 , wherein said carbon is in the form of nanotubes.

15. The material according to claim 12 , wherein said nanoparticles are selected from the group consisting of gold, silver, selenium, iron oxide, and titanium oxide.

16. A process of grafting the material of claim 1 with (thia)calix[n]aryl groups via their large rim, comprising grafting on the surface of the material as an ultra-thin layer of (thia)calix[n]aryl groups by electrochemical reduction, homogeneous reduction with a reactant, or thermal reduction of substituted (thia)calix[n]aryl salts of formula I:

wherein A − is an anion;

R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined in claim 1 ;

Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are each independently selected from the group consisting of OH, H, NO 2 , halogen, C 1-30 alkyl, acyl, carboxylic acid and derivatives thereof, —N 3 , alkenyl, alkynyl and N 2 + A − ; and

wherein a carbon of one arene ring of the (thia)calix[n]aryls is covalently and directly anchored to the material's surface.