SyntheticMetals 101 (1999) 514-515

Electronic Structure of New Donor Acceptor Substituted Chromophores

1) 21 1,3) 4) 4)
S. Schrader , H. Schiirmann , N. Koch , A.H. Otto , D. Prescher

Ii Universitiit Potsdum,Institut ftir Physik, Lehrstuhl Physik kondensierterMaterie, Am NeuenPalais IO, 14469 Potsdam, Germany
21Univ sit& Osnabriick, Fachbereich Physik, Adam und Eva Meyer StraJe 1234, 14567 Osnabriick, Germany
?I Technische Universittit Graz, Institut ftir Festkiirperphysik, Petersgasse16, SOIOGraz, Alc;tria
4) Instirut ftir Diinnschichttechnologie und Mikrosensorik TeEtow,KantstraFe55, 14513 Teitow

Abstract

We have carried out ultraviolet photoelectron spectroscopy(UPS) investigations at a synchrotron source (BESSY I) and quantum
chemical calculations in order to study correlations between chemical constitution and electronic structure of a series of conjugated
chromophores.Their n-electron system was modified by substitution with different donors tid acceptors at terminal positions, by
changing the molecular length, by introduction of different conjugated moieties into the central part of the molecules, and by
fluorination.

Ke.m+zords:
Sublimation, Photoelectron Spectroscopy,ConjugatedMolecules, Light Sources;Semi-empiricalModel CaIculations

1. Introduction Among these dyes are donor acceptor molecules like dimethyl-
amino nitro stilbene or modified azobenzenechromophores like
Ultraviolet photoelectron spectroscopy(UPS) is used for a study Disperse Red I which are used as very efficient dyes in organic
of correlations between chemical constitution and electronic nonlinear optics. For comparison also unsubstituted, symmetric
structureof linear conjugatedorganic dyes. molecules like azobenzeneor stilbene were-.studied.
For the present study a series of different chromophores was
synthesized. Their n-electron system was modified by
substitution with different acceptors and donors at terminal 2. Experimental
positions, by changing the molecular length and by introduction
of different conjugated moieties into the central pti of the Thin film samples were prepared by use of organic molecular
molecules. Another way of modification was the increase of beam deposition technique. Silicon 110 was chosen as substrate
fluorine content of the molecules changing the electronic material. The thickness of the deposited organic layers was
structure, and with respect to the application 5f these recordedduring the evaporation processusing a quartz oscillator
chromophores,both linear and non-linear optical properties as thickness monitor. As a result amorphousor polycrystalline films
well [l]. The basic chemical structure of the investigated with a typical thickness between 20 to 40 nm were obtained.
substancesis shown in Fig. 1. These samplesdid not show any charging phenomena during the
experiment The measurementswere done at the beam line
TGM2 at BESSY I using the spectrometer&DES 400. For each
sample experiments with the two different nominal photon
energiesof 60 eV and 40 eV, respectively, were carried out. The
angle of incidence of light was 20” to the normal direction of the
substrateplane. Photoelectronswere detectedat normal direction.
RI: -CF3 ,-NO2 , -H Angular dependent measurements have shown that the
evaporated layers did not show anisotropic emission as known
for thin adsorbedaromatic layers [2,3] or organized organic films
,CH3
R2: -N=NaN [41.
‘CH3 ’
,CH3
-N -N-NH, 3. Results
‘CH3 ’I CH2; 3
-H, -N’ Figure 2 presentsthe photoelectron spectra of four selecteddyes
‘CH2-CH2-OH measuredunder excitation with 60 eV phoTons. They show four
main peak groups A, B, C, and D centered at energies of about
X: N=N , CH=N , N=CH ,CH=CH -7 eV, -9 eV, -12 eV and -17 eV binding energy, respectively,
and a fifth peak at -19 eV obscured by the signal of secondary
Fig. 1. Basic structure of investigated dyes electrons. The chemical structure of the investigated chromo-
phores involves an acceptor part with the group Rl and a
0379-6779/99/S- seefront matter 0 1999 Elsevier ScienceS.A. All rights reserved.
PII: SO379-6779(98)01400-3
 S. Schrader et al. / Synrhetic Metals
donor part with the terminal group R2. Our experiments have
shown that a polarized binding part X with the azomethinegroup
at the donor part (Zi50) leads to a shift of peak A and B towards
lower binding energies. For azo dyes the strongest peak A shifts
slightly to higher binding energies. The differences between the
photoelectron spectra of azobenzene and of substituted azo-
benzeneare relatively small.
- F-79
\ X.N=N
?-‘--+-
X N=N
Rl,RZ H
1 I , spectra shown in figure 2 this peak is difficult to separatefrom
-15 -10 -5
BindingEnergy/ eV
Fig.2. UPS spectraof four selectedchromophores
For a better understanding of the measuredphotoelectron spectra
and in order to assign the different peaks to certain molecular
orbitals which take part in the photoelectron process we have
calculated the orbital structure by use of the program package
HyperChem [5]. One result is shown together with the measured
spectrum in fig. 3. For calculation the semiempirical method
PM3 was used. In order to carry out summation over all involved
states a gaussian line profile was assumed and the calculated
population of the molecular orbitals was taken into account.
.2n .I5 -10 -5
Binding Energy I eV
Fig.3. Experimental and calculated (PM3) UPS spectraof dye
F228, the structure is shown in Fig.4
F226
Fig.4. Chemical structure of the F228 dye
101 (1999) 514-515 51.5
The calculated spectrum reflects main features of the measured
photoelectron spectrum. Thus, the selected quantumchemical
method estimates both energy and population of molecular
orbitals in a sufficient manner.
From comparison of measured peaks with the results of
quantumchemical calculations we can conclude that the low
energy peak A near -7 eV is due to emission from n-orbitals. The
second peak group B at -9 eV, which is represented in the
calculated spectrum by two different peaks, involves emission
from o-states of C-C and C-H bonds. A further peak at -12 eV
(C) is given by the emission from higher energetic C-C o-states.
The main part of a fourth dominant peak D at binding energy of
-17 eV is characterized by the photoelectron emission of three
centre C-C-H o-orbitals in which only every secondC-H bond is
involved. Partial fluorination of the structures does not change
the general features of the UPS spectra. Only peak C is slightly
shifted to higher binding energies.The C-F bonds contribute not
only to peak C but also to peak D at -17 eV. The additional peak
near - 19 eV (not labelled) is connectedwith lower lying two and
three centre C-C-H, N-N or C-C-o-orbitals. In the experimental
0 the background signal.
4. Conclusion
The influence of the chemical structure of different chromo-
phores on the n-electron system was investigated by means of
ultraviolet photoelectron spectroscopy. The molecules were
modified by substitution with different acceptors and donors at
terminal positions, by changing the molecular length and by
introduction of different conjugated moieties into the central part.
In addition, quantum chemical calculations were performed in
order to study correlations between chemical constitution and
electronic structure of a series of conjugated chromophores. It
was found that the selectedquantum chemical method estimates
both energy and population of molecular orbitals in a sufficient
manner.
5. Acknowledgment
The work was supported by the BMBF under project number
03C 3005 and by EC under contract number FMRX-CT97-0106.
6. References
[l] S. Schrader,D. Prescher,SPIE Proceedings2968 (1997) 44
[2] M. Neuber, F. Schneider,C. Zubragel, M. Neumann, J.
Phys. Chem. 99 (1995) 9160
[3] H.H. Graen,M. Neuber, M. Neumann, G. Illing, H.J.
Freund, F.P. Netzer, Surf. Sci. 223 (1989) 33
[4] Chr. Zubragel, PhD Thesis University of Gottingen (1995)
[5] ProgramHyperChem, Release5.0 for Windows