IP Library Granted Patent US 9,450,191
Granted Patent B2
US 9,450,191 · App. 14/436,856 · Granted Sep 20, 2016

Thieno[2,3-C]Pyrrole-dione derivatives and their use for organic semiconductors

Inventors: Massimo Zambianchi (Cesena, IT); Laura Favaretto (Ozzano nell'Emilia, IT); Manuela Melucci (Bologna, IT); Michele Muccini (Bologna, IT); Raffaella Capelli (Bologna, IT)
Assignee: E.T.C. S.R.L.
H01L51/0071C07D495/04C09K11/06H01L51/00H01L51/0036H01L51/0068H01L51/0074C09K2211/1007C09K2211/1014C09K2211/1029C09K2211/1051C09K2211/1092H01L51/0545H01L51/0558H01L51/5296
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Quick Facts
Patent No.
US 9,450,191
App. No.
14/436,856
Granted
Sep 20, 2016
Kind
B2
Abstract

Compounds of formulae (I) and (II) useful as organic semiconductor materials, and semiconductor devices containing such organic semiconductor materials are described.

Claims (46)

1. A compound having formula (II):

wherein:

R 1 , R 2 , R 3 independently of each other, are selected from a group consisting of C 1 -C 6 linear alkyl groups, C 6 cycloalkyl groups, and C 6 unsubstituted and substituted monocyclic aryl groups;

R 4 and R 5 , independently of each other, are selected from a group consisting of hydrogen, and C 1 alkyl group,

Ar 1 , Ar 2 , Ar 3 and Ar 4 , independently of each other, are moieties selected from a group consisting of a C 6 unsubstituted and substituted monocyclic aryl groups, C 4 unsubstituted and substituted monocyclic heteroaryl groups, and C 6 unsubstituted and substituted polycyclic heteroaryl groups or combinations thereof as dimers, trimers and tetramers;

Z and Z′, independently of each other, are selected from a group consisting of bivalent radicals of formulas (III), (IV), (V), and (VI):

wherein G is selected from a group consisting of hydrogen, halogens, C 1 -C 20 linear or branched alkyl groups, C 2 -C 20 linear or branched alkenyl groups, C 2 -C 20 linear or branched alkynyl groups, C 1 -C 20 linear or branched heteroalkyl groups, C 2 -C 20 linear or branched heteroalkenyl groups, C 2 -C 20 linear or branched heteroalkynyl groups, C 3 -C 20 linear or branched cycloalkyl groups, C 3 -C 20 linear or branched heterocycloalkyl groups, C 2 -C 20 linear or branched alkylcarboxylic groups, C 2 -C 20 linear or branched alkylcarboxamide groups, C 2 -C 20 linear or branched alkylimino groups, C 1 -C 20 linear or branched alkylsulphonic groups, C 1 -C 20 linear or branched nitrile groups, C 6 -C 50 unsubstituted and substituted monocyclic aryl groups, C 10 -C 50 polycyclic aryl groups, C 10 -C 50 substituted polycyclic aryl groups, C 1 -C 50 unsubstituted and substituted monocyclic heteroaryl groups, C 6 -C 50 polycyclic heteroaryl groups, and C 6 -C 50 substituted polycyclic heteroaryl groups or combinations thereof;

s is 0 or 1;

n, m, r and t, independently of each other, are integers between 1 and 50;

q and f, independently of each other, are integers between 1 and 10; and

p is 0.

2. The compound according to claim 1 , having formula (IIa):

wherein R 1 , R 2 , R 4 , R 5 , Ar 1 , Ar 4 , Z, f, n, m are as specified in claim 1 .

3. The compound according to claim 1 , wherein q and f are each 1 or 2, and n, and m are between 2 and 10.

4. The compound according to claim 1 , wherein Z′ and/or Z are selected from a group consisting of ethynylene, cis-ethenylene and trans-ethenylene.

5. The compound according to claim 1 , wherein Ar 1 , Ar 2 , Ar 3 and/or Ar 4 , independently of each other, are selected from a group consisting of the following units (a), (b), (c), (d), (e), (f), (g), (h), (i), (l), (m), (n), (o), (p), (q), and (r):

wherein A is selected from a group consisting of S, O, Se, atoms and SO, SO 2 , R 14 —P═O, P—R 14 , N—R 15 , Si(R 15 ) 2 ) groups;

D is selected from a group consisting of C, S, O Se, atoms and SO, SO 2 , R 14 —P═O, P—R 14 , BR 14 , N—R 15 , Si(R 15 ) 2 groups;

B, C, independently of each other, are selected from a group consisting of C, N atoms;

E is selected from a group consisting of C(R 15 ) 2 , S, O, and NR 15 group;

R 8 , R 9 , R 10 , R 11 , R 12 and R 13 , independently of each other, are selected from a group consisting of hydrogen, halogens, C 1 -C 20 linear or branched alkyl groups, C 2 -C 20 linear or branched alkenyl groups, C 2 -C 20 linear or branched alkynyl groups, C 1 -C 20 linear or branched heteroalkyl groups, C 2 -C 20 linear or branched heteroalkenyl groups, C 2 -C 20 linear or branched heteroalkynyl groups, C 3 -C 20 linear or branched cycloalkyl groups, C 2 -C 20 linear or branched heterocycloalkyl groups, C 2 -C 20 linear or branched alkylcarboxylic groups, C 2 -C 20 linear or branched alkylcarboxamide groups, C 2 -C 20 linear or branched alkylimino groups, C 1 -C 20 linear or branched alkylsulphonic groups, C 1 -C 20 linear or branched nitrile groups, and C 5 -C 40 aryl groups, C 6 -C 40 alkylaryl groups;

R 14 , R 15 independently of each other, are selected from a group consisting of hydrogen, C 1 -C 20 linear or branched alkyl groups, C 2 -C 20 linear or branched alkenyl groups, C 2 -C 20 linear or branched alkynyl groups, C 1 -C 20 linear or branched heteroalkyl groups, C 2 -C 20 linear or branched heteroalkenyl groups, C 2 -C 20 linear or branched heteroalkynyl groups, C 3 -C 20 linear or branched cycloalkyl groups, C 3 -C 20 linear or branched heterocycloalkyl groups, C 2 -C 20 linear or branched alkylcarboxylic groups, C 2 -C 20 linear or branched alkylcarboxamide groups, C 2 -C 20 linear or branched alkylimino groups, C 1 -C 20 linear or branched alkylsulphonic groups, C 1 -C 20 linear or branched nitrile groups, C 5 -C 40 aryl groups, and C 6 -C 40 alkylaryl groups.

6. The compound according to claim 1 , wherein Ar 1 , Ar 2 , Ar 3 and/or Ar 4 , independently of each other, are selected from a group consisting of the following groups (s) and (t):

wherein A is selected from a group consisting of S, O, Se, atoms and SO, SO 2 , R 14 —P═O, P—R 14 , N—R 15 , Si(R 15 ) 2 groups;

W is a moiety selected from a group consisting of the units (a), (b), (c), (d), (e), (f), (g), (h), (i), (l), (m), (n), (o), (p), (q), and (r) of claim 5 ; and

R 16 is selected from a group consisting of hydrogen, halogens, C 1 -C 20 linear or branched alkyl groups, C 2 -C 20 linear or branched alkenyl groups, C 2 -C 20 linear or branched alkynyl groups, C 1 -C 20 linear or branched heteroalkyl groups, C 2 -C 20 linear or branched heteroalkenyl groups, C 2 -C 20 linear or branched heteroalkynyl groups, C 3 -C 20 linear or branched cycloalkyl groups, C 3 -C 20 linear or branched heterocycloalkyl groups, C 1 -C 20 linear or branched alkylcarboxylic groups, C 1 -C 20 linear or branched alkylcarboxamide groups, C 1 -C 20 linear or branched alkylimino groups, C 1 -C 20 linear or branched alkylsulphonic groups, C 1 -C 20 linear or branched nitrile groups, C 5 -C 40 aryl groups, and C 6 -C 40 alkylaryl groups.

7. The compound according to claim 1 , wherein Ar 1 , Ar 2 , Ar 3 and/or Ar 4 , independently of each other, are selected from a group consisting of the following formulas (u), (v), (w), (x) and (y):

wherein n is comprised between 2 and 10 and R 8 , R 9 , independently of each other, are selected from a group consisting of hydrogen, halogens, C 1 -C 20 linear or branched alkyl groups, C 2 -C 20 linear or branched alkenyl groups, C 2 -C 20 linear or branched alkynyl groups, C 1 -C 20 linear or branched heteroalkyl groups, C 2 -C 20 linear or branched heteroalkenyl groups, C 2 -C 20 linear or branched heteroalkynyl groups, C 3 -C 20 linear or branched cycloalkyl groups, C 2 -C 20 linear or branched heterocycloalkyl groups, C 2 -C 20 linear or branched alkylcarboxylic groups, C 2 -C 20 linear or branched alkylcarboxamide groups, C 2 -C 20 linear or branched alkylimino groups, C 1 -C 20 linear or branched alkylsulphonic groups, C 1 -C 20 linear or branched nitrile groups, C 5 -C 40 aryl groups, and C 6 -C 40 alkylaryl groups.

8. A compound having the following formula:

9. An organic semiconductor material in an electronic device comprising the compound according to claim 1 .

10. The organic semiconductor material in the electronic device according to claim 9 , wherein the organic semiconductor material is an n-type organic semiconductor material.

11. An electronic device comprising a semiconductor layer in contact with a number of electrodes, wherein the semiconductor layer includes at least one compound according to claim 1 .

12. A compound having formula (I):

wherein:

R 1 , R 2 , R 3 independently of each other, are selected from a group consisting of C 1 -C 6 linear alkyl groups, C 6 cycloalkyl groups, and C 6 unsubstituted and substituted monocyclic aryl groups;

Ar, Ar 1 , Ar 2 , Ar 3 and Ar 4 , independently of each other, are moieties selected from a group consisting of a C 6 unsubstituted and substituted monocyclic aryl groups, C 4 unsubstituted and substituted monocyclic heteroaryl groups, and C 6 unsubstituted and substituted polycyclic heteroaryl groups or combinations thereof as dimers, trimers and tetramers;

Z and Z′, independently of each other, are selected from a group consisting of bivalent radicals of formulas (III), (IV), (V), and (VI):

wherein G is selected from a group consisting of hydrogen, halogens, C 1 -C 20 linear or branched alkyl groups, C 2 -C 20 linear or branched alkenyl groups, C 2 -C 20 linear or branched alkynyl groups, C 1 -C 20 linear or branched heteroalkyl groups, C 2 -C 20 linear or branched heteroalkenyl groups, C 2 -C 20 linear or branched heteroalkynyl groups, C 3 -C 20 linear or branched cycloalkyl groups, C 3 -C 20 linear or branched heterocycloalkyl groups, C 2 -C 20 linear or branched alkylcarboxylic groups, C 2 -C 20 linear or branched alkylcarboxamide groups, C 2 -C 20 linear or branched alkylimino groups, C 1 -C 20 linear or branched alkylsulphonic groups, C 1 -C 20 linear or branched nitrile groups, C 6 -C 50 unsubstituted and substituted monocyclic aryl groups, C 10 -C 50 polycyclic aryl groups, C 10 -C 50 substituted polycyclic aryl groups, C 1 -C 50 unsubstituted and substituted monocyclic heteroaryl groups, C 6 -C 50 polycyclic heteroaryl groups, and C 6 -C 50 substituted polycyclic heteroaryl groups or combinations thereof;

s is 0 or 1;

n, m, r and t, independently of each other, are integers between 1 and 50;

q and f, independently of each other, are integers between 1 and 10; and

p is 0.

13. The compound according to claim 12 , having formula (Ia):

wherein R 1 , R 2 , Ar, Ar 1 , Ar 4 , Z, f, n, m are as specified in claim 12 .

14. The compound according to claim 12 , wherein q and f are each 1 or 2, and n, and m are between 2 and 10.

15. The compound according to claim 12 , wherein Z′ and/or Z are selected from a group consisting of ethynylene, cis-ethenylene and trans-ethenylene.

Assignments (9)
ASSET PURCHASE AGREEMENT Recorded Dec 13, 2025
From: FLEXTERRA, INC.; FLEXTERRA TAIWAN CORPORATION LIMITED
To: USINVEST, LLC
Reel/Frame 073948/0751 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 5, 2025
From: FLEXTERRA, INC.
To: USINVEST LLC
Reel/Frame 073464/0376 →
SECURITY INTEREST Recorded Oct 17, 2024
From: FLEXTERRA, INC.
To: SAES GETTERS INTERNATIONAL LUXEMBOURG S.A., IN ITS CAPACITY AS COLLATERAL AGENT
Reel/Frame 069191/0563 →
SECURITY INTEREST Recorded Aug 10, 2021
From: FLEXTERRA, INC.
To: SAES GETTERS INTERNATIONAL LUXEMBOURG S.A., IN ITS CAPACITY AS COLLATERAL AGENT
Reel/Frame 057136/0437 →
CHANGE OF NAME Recorded Nov 16, 2020
From: E.T.C. S.R.L.
To: E.T.C. S.R.L. IN LIQUIDAZIONE
Reel/Frame 054370/0092 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 8, 2020
From: E.T.C. IN LIQUIDAZIONE
To: FLEXTERRA, INC.
Reel/Frame 054004/0974 →
CHANGE OF ASSIGNEE'S ADDRESS Recorded Feb 1, 2017
From: E.T.C. S.R.L.
To: E.T.C. S.R.L.
Reel/Frame 041590/0071 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 2, 2016
From: CAPELLI, RAFFAELLA
To: E.T.C. S.R.L.
Reel/Frame 038595/0065 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 20, 2015
From: MELUCCI, MANUELA; FAVARETTO, LAURA; ZAMBIANCHI, MASSIMO; MUCCINI, MICHELE
To: E.T.C. S.R.L.
Reel/Frame 035452/0742 →
Priority Claims (1)
IT MI2012A1952 · Nov 16, 2012 · national
Continuity (1)
Related Publication 20150287932A1 · Oct 8, 2015