Segmented graphene nanoribbons

Patent metadata

Field	Value
Publication number	US-9975777-B2
Application number	US-201214357300-A
Country	US
Kind code	B2
Filing date	Nov 13, 2012
Priority date	Nov 14, 2011
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

The present invention relates to a segmented graphene nanoribbon, comprising at least two different graphene segments covalently linked to each other, each graphene segment having a monodisperse segment width, wherein the segment width of at least one of said graphene segments is 4 nm or less and to a method for preparing it by polymerizing at least one polycyclic aromatic monomer compound and/or at least one oligo phenylene aromatic hydrocarbon monomer compound to form at least one polymer and by at least partially cyclodehydrogenating the one or more polymer.

First claim

The invention claimed is:

1. A process for preparing the segmented graphene nanoribbon comprising:
at least two different graphene segments covalently linked to each other;
wherein each graphene segment has a monodisperse segment width;
wherein the segment width of at least one of the graphene segments is 4 nm or less, wherein said process comprises:
(a) depositing at least one polycyclic aromatic monomer compound and/or oligo phenylene aromatic hydrocarbon monomer compound on a solid substrate;
(b) polymerizing the polycyclic aromatic and/or oligo phenylene aromatic hydrocarbon monomer compound so as to form at least one polymeron the surface of the solid substrate; and
(c) at least partially cyclodehydrogenating the one or more polymers of (b).

2. The process of claim 1 , wherein each graphene segment of the segmented graphene nanoribbon has a monodisperse segment width of 4 nm or less.

3. The process of claim 1 , wherein each graphene segment has a repeating unit derived from at least one substituted or unsubstituted polycyclic aromatic monomer compound, and/or from at least one substituted or unsubstituted oligo phenylene aromatic hydrocarbon monomer compound.

4. The process of claim 3 , wherein the repeating units of different graphene segments differ in at least in one property selected from the group consisting of segment width, substituents attached to the repeating unit, degree of annelation of aromatic rings, degree of cyclodehydrogenation, and number of annelated aromatic rings.

5. The process of claim 1 , wherein each of the segments of the segmented graphene nanoribbon has a length in the range of 0.25 to 250 nm, and/or the total length of the segmented graphene nanoribbon is at least 4 nm.

6. The process of claim 1 , wherein the segments of the segmented graphene nanoribbon are in a linear arrangement, or at least one segment of the segmented graphene nanoribbon is covalently linked to at least three neighbouring segments.

7. The process of claim 1 , wherein at least one of the graphene segments has a substituted or unsubstituted repeating unit with Ni dimer lines across the segment width, and at least one of the graphene segments has a substituted or unsubstituted repeating unit with N2 dimer lines across the segment width, wherein N1=5 to 13, and N2=k×N1, with k=2, 3, or 4.

8. The process of claim 1 , wherein the two or more different graphene segments have repeating units which are derived from substituted or unsubstituted anthracene monomer compounds.

9. The process of claim 8 , wherein the segmented graphene nanoribbon has the structure Ia:

under the provision that at least two of m, x, n, y, o, z, and p are ≥1; and
m+x+n+y+o+z+p≥10;
and wherein
X are each independently H, a halogen, SH, SR 3 , OH, OR 3 , OSO 2 R 3 , (SO)R 3 , (SO 2 )R 3 , NR 1 R 2 , NO 2 , POR 3 R 3 , PO(OR 3 )R 3 , PO(OR 3 ) 2 , B(R 3 ) 2 , B(OR 3 ) 2 , (CO)R 3 , (CO)OR 3 ;
Y are each independently H or two Y together form a direct bond between neighbouring repeating units;
R are each independently hydrogen; linear or branched or cyclic C 1 -C 12 alkyl which is unsubstituted or substituted by one or more OH, C 1 -C 4 alkoxy, phenyl, or by CN; C 2 -C 12 alkyl which is interrupted by one or more non-consecutive O; halogen; OH; OR 3 ; SR 3 ; CN; NO 2 ; NR 1 R 2 ; (CO)R 3 ; (CO)OR 3 ; O(CO)OR 3 ; O(CO)NR 1 R 2 ; O(CO)R 3 ; C 1 -C 12 alkoxy; C 1 -C 12 alkylthio; (C 1 -C 6 alkyl)-NR 7 R 8 ; or —O—(C 1 -C 6 alkyl)NR 1 R 2 ; aryl or heteroaryl (wherein aryl is preferably phenyl, biphenyl, naphthyl, or anthryl all of which are unsubstituted or are substituted by one or more C 1 -C 4 -alkyl, CN, OR 3 , SR 3 , CH 2 OR 3 , (CO)OR 3 , (CO)NR 1 R 2 or halogen);
or two R together with the carbon atoms they are attached to form a 5-8-membered cycle or heterocycle;
R 1 and R 2 are each independently hydrogen, linear or branched C 1 -C 6 alkyl or phenyl, or R 1 and R 2 together with the nitrogen atom to which they are bonded to form a group selected from

and
R 3 is H, C 1 -C 12 alkyl, phenyl which is unsubstituted or is substituted by one or more C 1 -C 4 alkyl, phenyl, halogen, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio.

10. The process of claim 1 , wherein two or more different graphene segments have repeating units which are derived from substituted or unsubstituted pentacene monomer compounds.

11. The process of claim 10 , wherein the segmented graphene nanoribbon has the structure II:

under the provision that at least two of m, x, n, y, o, z, and p are ≥1;
wherein m+x+n+y+o+z+p≥10;
and wherein
X are each independently H, a halogen, SH, SR 3 , OH, OR 3 , OSO 2 R 3 , (SO)R 3 , (SO 2 )R 3 , NR 1 R 2 , NO 2 , POR 3 R 3 , PO(OR 3 )R 3 , PO(OR 3 ) 2 , B(R 3 ) 2 , B(OR 3 ) 2 , (CO)R 3 , (CO)OR 3 ;
Y are each independently H or two Y together form a direct bond between neighbouring repeating units;
R are each independently hydrogen; linear or branched or cyclic C 1 -C 12 alkyl which is unsubstituted or substituted by one or more OH, C 1 -C 4 alkoxy, phenyl, or by CN; C 2 -C 12 alkyl which is interrupted by one or more non-consecutive O; halogen; OH; OR 3 ; SR 3 ; CN; NO 2 ; NR 1 R 2 ; (CO)R 3 ; (CO)OR 3 ; O(CO)OR 3 ; O(CO)NR 1 R 2 ; O(CO)R 3 ; C 1 -C 12 alkoxy; C 1 -C 12 alkylthio; (C 1 -C 6 alkyl)-NR 7 R 8 ; or —O—(C 1 -C 6 alkyl)NR 1 R 2 ; aryl or heteroaryl (wherein aryl is preferably phenyl, biphenyl, naphthyl, or anthryl all of which are unsubstituted or are substituted by one or more C 1 -C 4 -alkyl, CN, OR 3 , SR 3 , CH 2 OR 3 , (CO)OR 3 , (CO)NR 1 R 2 or halogen);
or two R together with the carbon atoms they are attached to form a 5-8-membered cycle or heterocycle;
R 1 and R 2 are each independently hydrogen, linear or branched C 1 -C 6 alkyl or phenyl, or R 1 and R 2 together with the nitrogen atom to which they are bonded to form a group selected from

and
R 3 is H, C 1 -C 12 alkyl, phenyl which is unsubstituted or is substituted by one or more C 1 -C 4 alkyl, phenyl, halogen, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio.

12. The process of claim 1 , wherein two or more different graphene segments have repeating units which are derived from substituted or unsubstituted anthracene and pentacene monomer compounds.

13. The process of claim 12 , wherein the segmented graphene nanoribbon has the structure IV:

wherein m+n≥10,
and wherein
X are each independently H, a halogen, SH, SR 3 , OH, OR 3 , OSO 2 R 3 , (SO)R 3 , (SO 2 )R 3 , NR 1 R 2 , NO 2 , POR 3 R 3 , PO(OR 3 )R 3 , PO(OR 3 ) 2 , B(R 3 ) 2 , B(OR 3 ) 2 , (CO)R 3 , (CO)OR 3 ;
R are each independently hydrogen; linear or branched or cyclic C 1 -C 12 alkyl which is unsubstituted or substituted by one or more OH, C 1 -C 4 alkoxy, phenyl, or by CN; C 2 -C 12 alkyl which is interrupted by one or more non-consecutive O; halogen; OH; OR 3 ; SR 3 ; CN; NO 2 ; NR 1 R 2 ; (CO)R 3 ; (CO)OR 3 ; O(CO)OR 3 ; O(CO)NR 1 R 2 ; O(CO)R 3 ; C 1 -C 12 alkoxy: C 1 -C 12 alkylthio; (C 1 -C 6 alkyl)-NR 7 R 8 ; or —O—(C 1 -C 6 alkyl)NR 1 R 2 ; aryl or

Assignees

• Basf Se
• Empa Materials Science And Tech

Inventors

• Fasel Roman
• Ruffieux Pascal
• Muellen Klaus
• Blankenburg Stephan
• Cai Jinming
• Feng Xinliang
• Pignedoli Carlo
• Passerone Daniele

Classifications

• Y10T428/298

  Physical dimension · CPC title

• C08G2261/314

  Condensed aromatic systems, e.g. perylene, anthracene or pyrene · CPC title

• C08G61/10

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title

• C01B2204/065

  characterized by their width or by their aspect ratio · CPC title

• C01B2204/06

  Graphene nanoribbons · CPC title