Soluble alkyl (
II,
8a,b), fluoroalkyl (
4a), and fluoroalkoxy (
4b,c,
8c) 1,(4)- or 2,(3)-substitutedphthalocyaninato- and linear 2,(3)- and an
gular 1,(2)-annulated naphthalocyaninatotitanium(IV) oxides
10,
12, and
14 were synthesized and characterized with re
gard to their spectroscopic, photophysical, andphotochemical properties. While alkyl- and fluoroalkoxy-substituted compounds are hi
ghly soluble in nonpolarsolvents, e.
g., hexane, fluoroalkyl-substituted compounds are better soluble in polar aprotic solvents such asacetone. The stability a
gainst photooxidation in solution is enhanced on
goin
g from alkylated phthalocyanines1,(4)-(C
5H
11)
8PcTiO (
8a), 1,(4)-(C
6H
13)
8PcTiO (
8b), and 2,(3)-(C
4H
9)
8PcTiO (
II) to fluorinated phthalocyanines2,(3)-(CF
3)
4PcTiO (
4a), 2,(3)-(CF
3CH
2O)
4PcTiO (
4b), and 2,(3)-(CF
3CH
2O)
8PcTiO (
4c), from phthalocyaninesto naphthalocyanines (
tert-butyl)
4-2,(3)-NcTiO (
10), 1,(2)-NcTiO (
12), and (
tert-butyl)
4-1,(2)-NcTiO (
14), andon
goin
g from 2,(3)-substituted
4a-
c to 1,(4)-substituted phthalocyanines
8a-
c. Thin films of these compounds,prepared by either vacuum deposition or spin castin
g, are classified into three types accordin
g to increasin
gintermolecular
ges/
gifchars/pi.
gif" BORDER=0 >-
ges/
gifchars/pi.
gif" BORDER=0 > interactions. Type
ges/
gifchars/alpha.
gif" BORDER=0> films, characterized by absence of exciton splittin
g, are formedfrom 1,(4)-substituted phthalocyanines
8a-
c. These films show low dark conductivities and photoconductivitiesand are considerably sensitive to photooxidation. Type
ges/
gifchars/beta2.
gif" BORDER=0 ALIGN="middle"> films, characterized by weak exciton splittin
g, areformed from fluorinated phthalocyanines
4a-
c as well as from rapidly deposited 2,(3)-substituted phthalocyanines
II and the unsubstituted PcTiO (
I). These films show enhanced photoconductivity and are
generallymore stable a
gainst photooxidation than type
ges/
gifchars/alpha.
gif" BORDER=0> films. Type
ges/
gifchars/
gamma.
gif" BORDER=0 > films, formed by slow deposition of
II, 10 andunsubstituted phthalocyanine
I, are classified by a lar
gely red-shifted B-band absorbin
g in the near-IR. Thesefilms are hi
ghly photosensitive as well as stabilized a
gainst photooxidation. Steady-state photoconductivitiesand dark conductivities in thin films are stron
gly dependent on oxy
gen partial pressure. Alkylated PcTiO'ssuch as
8a,
8b, and
II are found to be p-type conductors (positive oxy
gen influence on conductivities) likeunsubstituted PcTiO (
I), whereas an
gularly annulated naphthalocyanines such as
12 and
14 as well as fluorinatedPcTiO's
4a-
c are n-type conductors (ne
gative oxy
gen influence on conductivity). These findin
gs arerationalized by comparison with experimental and theoretical literature data.