Multiply fused porphyrin polymer film coated on a substrate

Patent metadata

Field	Value
Publication number	US-2023311157-A1
Application number	US-202118013632-A
Country	US
Kind code	A1
Filing date	Jun 29, 2021
Priority date	Jun 29, 2020
Publication date	Oct 5, 2023
Grant date	—

Abstract

A multiply fused, conjugated, porphyrin polymer film coated on a substrate, wherein the porphyrin monomer repeating units are di-meso-substituted porphyrins; and including a metal cation selected from the group consisting of Mg(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(II), Pd(II), Ag(II), Pt(II) and Au(III), or mixtures thereof; the porphyrin units are multiply fused, including doubly-fused and/or triply-fused; including a substituent R attached to the meso position of the porphyrin monomer, the substituent R being an aromatic group presenting at least one free ortho position among; at least one of the two free ortho positions of the aromatic substituent is fused to the 13 position of the porphyrin monomer, the porphyrin polymer film being a porous porphyrin polymer film with mean pore diameters within the range of from 2 nm to 100 nm, and exhibiting a density not greater than 2 g/cm 3 . The invention also relates to a process for obtaining the multiply fused porphyrin polymer film coated on a substrate.

First claim

What is claimed is:

1 .- 13 . (canceled)

14 . A multiply fused, conjugated, porphyrin polymer film coated on a substrate, said multiply fused porphyrin polymer being of formula (I)

wherein:
“n” is an integer greater than 1;
the porphyrin monomer repeating units are di-meso-substituted porphyrins;
M is a metal cation selected from the group consisting of Mg(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(II), Pd(II), Ag(II), Pt(II) and Au(III), or mixtures thereof;
the porphyrin units are multiply fused, including doubly-fused and/or triply-fused;
each substituent R attached to the meso position of the porphyrin monomer is an aromatic group presenting at least one free ortho position among; and
at least one of the two free ortho positions of the aromatic substituent R is fused to the β position of the porphyrin monomer,
wherein the porphyrin polymer film is a porous porphyrin polymer film with mean pore diameters, determined by SEM, within the range of from 2 nm to 100 nm, and exhibiting a density, calculated from a measured surface density and the thickness of the film, not greater than 2 g/cm 3 .

15 . The multiply fused, conjugated, polymer porphyrin film coated on a substrate according to claim 14 , wherein the porphyrin monomer units are multiply fused, including one of doubly-fused β-meso, meso-β, and triply-fused β-β, meso-meso, β-β.

16 . The multiply fused, conjugated, polymer porphyrin film coated on a substrate according to claim 14 , wherein M is selected from at least one of Co(II) and Cu(II).

17 . The multiply fused, conjugated, polymer porphyrin film coated on a substrate according to claim 14 , wherein the mean pore diameters is within the range of from 5 nm to 80 nm, and, independently, the density is of from 0.20 g/cm 3 to 1.5 g/cm 3 .

18 . The multiply fused, conjugated, polymer porphyrin film coated on a substrate according to claim 14 , wherein the n value of the porphyrin repeating units is from 2 to 50.

19 . The multiply fused, conjugated, polymer porphyrin film coated on a substrate according to claim 14 , presenting at least one of the following characteristics:
a thickness of from 500 nm to 10 μm; an electrical conductivity of from 10 −4 S/cm to 10 S/cm; a Young modulus of from 1 GPa to 3 GPa; and a water uptake of from 0.5 mg/mm 3 of H 2 O to 1.0 mg/mm 3 of H 2 O.

20 . The multiply fused, conjugated, polymer porphyrin film coated on a substrate according to claim 14 , wherein the aromatic group R is a 6-membered aromatic ring structure selected from the group consisting of at least one of phenyl, 4-pyridyl, 3-pyridyl, 4-methylphenyl (p-tolyl), 3,5-di-tert-butylphenyl, 4-hydroxyphenyl, 4-carboxyphenyl, 4-aminophenyl, 3-cyanophenyl, 4-trifluoromethyl-phenyl, 4-fluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-chlorophenyl, 4-bromophenyl, naphthalene, anthracene, phenanthrene and pyrene.

21 . A process for forming, on a substrate, a multiply fused, conjugated, porphyrin polymer being of formula (I)

wherein:
“n” is an integer greater than 1;
the porphyrin monomer repeating units are di-meso-substituted porphyrins;
M is a metal cation selected from the group consisting of Mg(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(II), Pd(II), Ag(II), Pt(II) and Au(III), or mixtures thereof;
the porphyrin units are multiply fused, including doubly-fused and/or triply-fused;
each substituent R attached to the meso position of the porphyrin monomer is an aromatic group presenting at least one free ortho position among; and
at least one of the two free ortho positions of the aromatic substituent R is fused to the β position of the porphyrin monomer,
wherein the porphyrin polymer film is a porous porphyrin polymer film with mean pore diameters, determined by SEM, within the range of from 2 nm to 100 nm, and exhibiting a density, calculated from a measured surface density and the thickness of the film, not greater than 2 g/cm 3 ,
the method comprising the steps of:
providing a substrate in a vacuum chamber,
performing on the substrate an oxidative chemical vapour deposition reaction with a predetermined quantity of at least one oxidant selected from FeCl 3 , CuCl 2 and Cu(ClO 4 ) 2 , and a predetermined quantity of at least one porphyrin monomer of general formula (II):

wherein
M is a metal cation selected from the group consisting of Mg(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(II), Pd(II), Ag(II), Pt(II) and Au(III), or mixtures thereof;
each substituent R attached to the meso position of the porphyrin monomer is an aromatic group presenting at least one free ortho position;
wherein step (b) is carried at a substrate temperature range of from 150° C. to 250° C., and in that the ratio (r) of the at least one oxidant quantity/at least one porphyrin monomer quantity is within a range of from 35 to 150.

22 . The process according to claim 21 , wherein the r range is of from 45 to 125.

23 . The process according to claim 21 , wherein the temperature range of the substrate is of from 150° C. to 225° C.

24 . The process according to claim 21 , wherein step b) is further performed with at least one of:
a crosslinking monomer being a mono-meso-substituted metalloporphyrin and/or an unsubstituted metalloporphyrin; and an octa-β-substituted metalloporphyrin which central metal cation is selected from the group consisting of at least one of Mg(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(II), Pd(II), Ag(II), Pt(II) and Au(III).

Assignees

• Luxembourg Inst Science & Tech List

Inventors

• Boscher Nicolas
• Baba Kamal
• Bengasi Giuseppe
• Huerta Flores Ali Margot

Classifications

• B05D1/60 Primary

  Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00) · CPC title

• C09D147/00

  Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers (C09D145/00 takes precedence; based on conjugated diene rubbers C09D109/00 - C09D121/00) · CPC title

• C09D7/61

  inorganic · CPC title

• B05D3/002

  Pretreatement · CPC title

• B05D5/12

  to obtain a coating with specific electrical properties · CPC title