Hetero-spiro compounds and their use as electroluminescence...

Details Hetero-spiro compounds and their use as electroluminescence... Hetero-spiro compounds and their use as electroluminescence...

1997-05-22

2001-12-11

Yamnitzky, Marie (Department: 1774)

Stock material or miscellaneous articles

Composite

Of inorganic material

C428S917000, C313S504000, C252S301160, C556S081000, C556S087000, C556S400000, C556S406000, C556S407000, C556S426000

Reexamination Certificate

active

06329082

ABSTRACT:

DESCRIPTION
There is a great industrial need for large-area solid-state light sources for a series of applications, predominantly in the field of display elements, VDU technology and lighting engineering. The demands made of these light sources can at present not be completely satisfactorily met by any of the existing technologies.
As an alternative to the conventional display elements, such as incandescent lamps, gas-discharge lamps and non-self-illuminating liquid crystal display elements, knowledge has existed for some time of electroluminescence (EL) materials and devices, such as light-emitting diodes (LEDs).
Electroluminescence materials are materials which are capable of radiating light on application of an electric field. The physical model for describing this effect is based on the radiative recombination of electrons and electron gaps (holes). In light-emitting diodes, the charge carriers are injected via the cathode or anode into the electroluminescence material. Electroluminescence devices comprise a luminescence material as light-emitting layer. Electroluminescence materials and devices are generally described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol A9, 5th Ed. VCH Verlag 1987 and the literature cited therein. Apart from inorganic materials, such as ZnS/Mn or GaAs, organic compounds have also become known as EL materials. A description of EL devices comprising low molecular weight organic EL materials is given, for example, in U.S. Pat. No. 4,539,507.
Disadvantages of these low molecular weight organic materials are, for example, the unsatisfactory film-forming properties and a pronounced tendency to crystallize.
Recently, polymers have also been described as EL materials (see, for example, WO-A 90/13148). However, the light yield (quantum efficiency) of these materials is considerably lower than for low molecular weight compounds.
It was desirable to find EL materials which have good light yields, at the same time can be processed into thin homogeneous films and have a low tendency to crystallize.
It has now surprisingly been found that hetero-spiro compounds have excellent suitability as EL materials. Spiro compounds have at least one tetravalent Spiro atom which links two ring systems to one another. This is described in detail in Handbook of Chemistry and Physics, 62nd edition (1981-2), pp. C-23 to 25.
Individual compounds of this type are described, for example, in U.S. Pat. No. 5,026,894, J. M. Tour et al., J. Am. Chem. Soc. 112 (1990) 5662 and J. M. Tour et al., Polym. Prepr. (1990) 408 as linkage elements for polymeric, organic semiconductors and have been proposed as materials for molecular electronics. However, possible use as EL materials cannot be derived therefrom.
The invention accordingly provides for the use of hetero-spiro compounds of the formula (I),
where
&PSgr; is an element of the 4th main group of the Periodic Table with the exception of carbon, preferably Sn, Ge or Si, particularly preferably Ge or Si, and
K
1
and K
2
are, independently of one another, conjugated systems, in electroluminescence devices.
Compounds of the formula (I) have good solubility in customary organic solvents, improved film-forming properties and a significantly reduced tendency to crystallize. This makes the production of electroluminescence devices easier and increases their life. The emission properties of the compounds used according to the invention can be adjusted across the entire range of the visible spectrum by selection of suitable substituents. In addition, the covalently bound arrangement of the two parts of the spiro compound allows a molecular structure such that certain properties can be set independently in the two halves of the molecule. Thus, one half can have, for example, charge transport or charge injection properties, while the other half has light-emitting properties. The spatial proximity of the two halves fixed by the covalent linkage is here favorable for energy transmission (see, for example, B. Liphardt, W. Lüttke, Liebigs Ann. Chem. 1981, 1118).
Preferred compounds of the formula (I) are hetero-spiro compounds of the formula (II),
where the symbols and indices have the following meanings:
gs:
&PSgr; is Si, Ge, Sn;
D, E, F, G are identical or different and are —CR
1
R
2
—, —O—, —S—, —NR
3
— or a chemical bond;
U, V are identical or different and are —CR
1
R
2
—, —O—, —S—, —NR
3
—, —SiR
1
R
2
—, —SO
2
—, —CO—, —CR
4
═CR
5
— or a chemical bond, with the proviso that either U or V is —CR
1
═CR
2
— or a chemical bond;
T is —O—, —S—, —NR3—, —CR
1
R
2
—, —CH═N—, —CA
5
═CA
6
—, —CH═CA
7
—, preferably —CH═CH—;
K, L, M, Q are identical or different, cyclic or acyclic hydrocarbon radicals which have conjugated electron systems and can also contain heteroatoms such as oxygen, nitrogen and/or sulfur;
A
1
, A
2
, A
3
, A
4
can be identical or different and have the same meanings as K, L, M, Q or are hydrogen, fluorine or a hydrocarbon radical having from 1 to 22, preferably from 1 to 15, carbon atoms which can also contain heteroatoms such as oxygen, nitrogen, silicon or fluorine; preferably a linear, branched and/or ring-containing alkyl, alkoxy, or alkyloxycarbonyl group, —CF
3
, —CN, —NO
2
, —NR
6
R
7
, —Ar or —O—Ar;
A
6
is hydrogen
A
5
and A
7
arc identical or different and are the values for B herein defined below with respect to formula (IV).
R
1
, R
2
, R
3
are identical or different and are H or a hydrocarbon radical having from 1 to 12 carbon atoms, where R
1
and R
2
can together also form an unsubstituted or substituted ring;
R
4
, R
5
are identical or different and have the same meanings as R
1
, R
2
, R
3
or are fluorine or —CF
3
;
R
6
, R
7
are identical or different and are H or a hydrocarbon radical having from 1 to 22 carbon atoms which can be aliphatic or aromatic, linear or branched and can also contain alicyclic elements, preferably methyl, ethyl, t-butyl, cyclohexyl, 3-methylphenyl; or R
6
and R
7
together form a ring,
Ar is an aromatic radical having up to 22 carbon atoms, preferably phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these aromatic radicals can be substituted by one or two groups R
4
, R
5
;
Q and A
1
, K and A
2
, L and A
3
, M and A
4
can, independently of one another, also each be joined together to form a ring which can be saturated, partially unsaturated or have maximum unsaturation, with a fused aromatic ring system preferably being present.
Particular preference is given to hetero-spirobifluorene derivatives of the formula (III),
where the symbols and indices have the following meanings:
&PSgr; is Si or Ge;
K, L, M, Q, A are identical or different and are
and A can also be identical or different and have the same meanings as R;
R can be identical or different and have the same meanings as K, L, M, Q or is —H, a linear or branched alkyl, alkoxy or ester group having from 1 to 22, preferably from 1 to 15, particularly preferably from 1 to 12, carbon atoms, —CN, —NO
2
, —NR
2
R
3
, —Ar or —O—Ar;
Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these groups can bear one or two radicals R,
m, n, p are, independently of one another, identical or different and are 0, 1, 2 or 3;
X, y are identical or different and are CR, N;
Z is —O—, —S—, —NR
1
—, -CR
1
R
4
—, —CH═CH—, —CH═N—;
R
1
, R
4
can be identical or different and have the same meanings as R;
R
2
, R
3
are identical or different and are H, a linear or branched alkyl group having from 1 to 22 carbon atoms, —Ar, 3-methylphenyl.
Preferred compounds of the formula (III) are those of the formulae (IIIa)-(IIIg)
IlIa) K=L=M=Q and are selected from the group consisting of:
R=C
1
-C
22
-alkyl, (CH
2
)
x
—SO
3
−
where x=2, 3 or 4
IIIb) K=M=H and Q=L and are selected from the group consisting of:
IIIc) K=M and are selected from the group consisting of:
R=C
1
-C
22
-alkyl, (CH
2
)
x
—SO
3
−
where x=2, 3 or 4 and Q=L an

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