IP Library › Granted Patent US 9,425,413
Granted Patent B2
US 9,425,413 · App. 14/672,124 · Granted Aug 23, 2016

Conjugated side-strapped phthalocyanines and methods for producing and using the same

Inventors: Dominic V. McGrath (Tucson, AZ); Neal R. Armstrong (Tucson, AZ)
Assignee: The Arizona Board of Regents on Behalf of the University of Arizona
H01L51/0078C07D487/22H01L51/4253Y02E10/549
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 9,425,413
App. No.
14/672,124
Granted
Aug 23, 2016
Kind
B2
Abstract

The present invention provides conjugated side-strapped phthalocyanines and methods for producing and using the same. In one particular embodiment, the conjugated side-strapped phthalocyanine is of the formula: where each of the substituents are defined herein.

Claims (65)

1. A conjugated side-strapped phthalocyanine compound of the formula:

wherein

M is a phthalocyanine coordinating moiety;

at least one pair of R W1 and R W2 , or R N1 and R N2 , or R E1 and R E2 , or R S1 and R S2 form a conjugated side-strapped substituent and the remaining are independently selected from the group consisting of:

(i) H;

(ii) C 1 -C 25 alkyl;

(iii) a moiety of the formula: —(CH 2 CH 2 O) a —(CH 2 ) b OR a1 , —(CH 2 CH 2 O) a —(CH 2 ) b NR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CONR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CN, —(CH 2 CH 2 O) a —(CH 2 ) b Cl, —(CH 2 CH 2 O) a —(CH 2 ) b Br, —(CH 2 CH 2 O) a —(CH 2 ) b I, —(CH 2 CH 2 O) a —(CH 2 ) b -Phenyl, or —(CH 2 CH 2 O) a —(CH 2 ) b -ethynyl;

(iv) an aryl or a heteroaryl group of the formula

wherein E is S, O, or NH, and R F1 , R F2 , R F3 , R F4 , R F5 , R F6 , R F7 , and R F8 are independently selected from the group consisting of:

(a) H;

(b) C 1 -C 25 alkyl;

(c) a moiety of the formula: —(CH 2 CH 2 O) a —(CH 2 ) b OR a1 , —(CH 2 CH 2 O) a —(CH 2 ) b NR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CONR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CN, —(CH 2 CH 2 O) a —(CH 2 ) b Cl, —(CH 2 CH 2 O) a —(CH 2 ) b Br, —(CH 2 CH 2 O) a —(CH 2 ) b I, —(CH 2 CH 2 O) a —(CH 2 ) b -Phenyl, or —(CH 2 CH 2 O) a —(CH 2 ) b -ethynyl;

(d) —NR e1 R e2 , —OR e3 , and —SR e4 ;

(e) an aryl or heteroaryl group; and

(f) a polymerizable group;

(v) a fused aromatic ring of the formula:

(vi) a polymerizable group selected from the group consisting of vinyl, allyl, 4-styryl, acryloyl, methacroyl, epoxide, acrylonitrile, isocyanate, isothiocyanate, strained ring olefins; —(CH 2 ) d SiCl 3 , —(CH 2 ) d Si(OCH 2 CH 3 ) 3 , and —(CH 2 ) d Si(OCH 3 ) 3 ;

(vii) halide; and

(viii) —NR e1 R e2 , —OR e3 , or —SR e4 ;

each of R A1 , R A2 , R B1 , R B2 , R C1 , R C2 , R D1 and R D2 is independently selected from the group consisting of:

(i) H;

(ii) C 1 -C 25 alkyl;

(iii) a moiety of the formula: —(CH 2 CH 2 O) a —(CH 2 ) b OR a1 , —(CH 2 CH 2 O) a —(CH 2 ) b NR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CONR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CN, —(CH 2 CH 2 O) a —(CH 2 ) b Cl, —(CH 2 CH 2 O) a —(CH 2 ) b Br, —(CH 2 CH 2 O) a —(CH 2 ) b I, —(CH 2 CH 2 O) a —(CH 2 ) b -Phenyl, —(CH 2 CH 2 O) a —(CH 2 ) b -ethynyl;

(iv) an aryl or heteroaryl group of the formula

wherein E is S, O, or NH, and R F1 , R F2 , R F3 , R F4 , R F5 , R F6 , R F7 , and R F8 are independently selected from the group consisting of:

(a) H;

(b) C 1 -C 25 alkyl;

(c) a moiety of the formula: —(CH 2 CH 2 O) a —(CH 2 ) b OR a1 , —(CH 2 CH 2 O) a —(CH 2 ) b NR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CONR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CN, —(CH 2 CH 2 O) a —(CH 2 ) b Cl, —(CH 2 CH 2 O) a —(CH 2 ) b Br, —(CH 2 CH 2 O) a —(CH 2 ) b I, —(CH 2 CH 2 O) a —(CH 2 ) b -Phenyl, or —(CH 2 CH 2 O) a —(CH 2 ) b -ethynyl;

(d) —NR e1 R e2 , —OR e3 , and —SR e4 ;

(e) an aryl or heteroaryl group; and

(f) a polymerizable group;

(v) a fused aromatic ring of the formula:

(vi) a polymerizable group selected from the group consisting of vinyl, allyl, 4-styryl, acryloyl, methacroyl, epoxide, acrylonitrile, isocyanate, isothiocyanate, strained ring olefins; —(CH 2 ) d SiCl 3 , —(CH 2 ) d Si(OCH 2 CH 3 ) 3 , and —(CH 2 ) d Si(OCH 3 ) 3 ;

(vii) halide;

(viii) —NR e1 R e2 , —OR e3 , or —SR e4 ;

or each pair of R A1 and R A2 , R B1 and R B2 , R C1 and R C2 , and R D1 and R D2 along with the carbon atom to which they are attached to form an optionally substituted phenyl ring moiety;

a is an integer from 0 to 10;

b is an integer from 1 to 25;

d is an integer between 0 and 25;

each of R e1 , R e2 , R e3 , and R e4 is independently selected from the group consisting of:

(a) H;

(b) C 1 -C 25 alkyl;

(c) a moiety of the formula: —(CH 2 CH 2 O) a —(CH 2 ) b OR a1 , —(CH 2 CH 2 O) a —(CH 2 ) b NR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CONR a2 R a3 , —(CH 2 CH 2 O) a —(CH 2 ) b CN, —(CH 2 CH 2 O) a —(CH 2 ) b Cl, —(CH 2 CH 2 O) a —(CH 2 ) b Br, —(CH 2 CH 2 O) a —(CH 2 ) b I, —(CH 2 CH 2 O) a —(CH 2 ) b -Phenyl, or —(CH 2 CH 2 O) a —(CH 2 ) b -ethynyl;

(d) an aryl or heteroaryl group; and

(e) a polymerizable group; and

each of R a1 , R a2 , and R a3 is independently selected from the group consisting of H, C 1 -C 25 alkyl and aryl.

2. The conjugated side-strapped phthalocyanine compound according to claim 1 , wherein said conjugated side-strapped substituent is a moiety of the formula:

wherein each of R 1 and R 2 is independently hydrogen, C 1 -C 25 alkyl and C 1 -C 25 haloalkyl;

or R 1 and R 2 together with the carbon atom to which they are attached to form aryl, heteroaryl, or heterocyclyl ring structure, each of which is optionally substituted.

3. The conjugated side-strapped phthalocyanine compound according to claim 2 of the formula:

wherein

M, R N1 , R N2 , R S1 , R S2 , R A1 , R A2 , R B1 , R B2 , R C1 , R C2 , R D1 and R D2 are those defined in claim 1 ;

each of R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 2c , R 2d , R 3a and R 4a is independently selected from the group consisting of hydrogen, C 1 -C 25 alkyl and C 1 -C 25 haloalkyl;

each of n 1 , n 2 and n 3 is independently 0 or 1; and

X is O or S.

4. The conjugated side-strapped phthalocyanine compound of claim 3 , wherein M comprises an element selected from the group consisting of vanadium, indium, gallium, aluminum, titanium, tin, lead, bismuth, manganese, and phosphorus.

5. An electronic device comprising a thin film of a compound of claim 1 .

6. The electronic device of claim 5 , wherein said electronic device comprises an optoelectronic device, a photovoltaic, a semi-conductor, a solar cell, a field-effect transistor, organic light emitting diode, or a combination thereof.

7. A composition comprising a conjugated side-strapped phthalocyanine compound having 2-fold symmetry and a solubility in tetrahydrofuran (THF) of at least 0.5±0.1 mole/L.

8. The composition according to claim 7 , wherein said conjugated side-strapped phthalocyanine compound has a solubility in chloroform of at least 0.5±0.1 mole/L.

9. The composition according to claim 7 , wherein said conjugated side-strapped phthalocyanine compound has a solubility in pyridine of at least 0.5±0.1 mole/L.

10. The composition according to claim 7 , wherein said composition comprises a thin film of said conjugated side-strapped phthalocyanine compound.

11. The composition according to claim 10 , wherein the hole mobility within said thin film is at least 0.10±0.02 cm 2 V −1 s −1 .

12. The composition according to claim 10 , wherein the hole mobility within said thin film is at least 0.90±0.18 cm 2 V −1 s −1 .

13. The composition according to claim 10 , wherein said thin film comprises ABAB stacking of said conjugated side-strapped phthalocyanine compound.

Assignments (2)
CONFIRMATORY LICENSE Recorded Mar 9, 2020
From: UNIVERSITY OF ARIZONA
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 052123/0430 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 2, 2015
From: MCGRATH, DOMINIC V.; ARMSTRONG, NEAL R.
To: THE ARIZONA BOARD OF REGENTS ON BEHALF OF THE UNIVERSITY OF ARIZONA
Reel/Frame 037195/0212 →
Continuity (2)
Provisional Application 61972230 · Mar 29, 2014
Related Publication 20150280143A1 · Oct 1, 2015