4th EucheMs chemistry congress

Poster Session 1
s969
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - inorganic Chemistry
P - 0 2 1 6
PhotoCheMiCAL, PhotoPhySiCAL And
BioLoGiCAL ProPertieS of noveL wAter
SoLuBLe PhthALoCyAnineS BeArinG
trifLuoroMethyLquinoLine GrouPS
d. evren 1 , A. KALKAn BurAt 1 , M. durMuS 2 ,
B. S. SeSALAn 1
1 Istanbul Technical University, Chemistry, Istanbul, Turkey
2 Gebze Institute of Technology, Chemistry, Istanbul, Turkey
Email: evren@itu.edu.tr, kalkanayf@itu.edu.tr,
sungurs@itu.edu.tr, durmus@gyte.edu.tr
For photodynamic therapy (PDT), a combination of a
photosensitizing drug and light in the presence of molecular
oxygen is used to obtain a therapeutic effect, and has been
proposed as an alternative treatment to complement conventional
protocols in the management of malignant tumours and many
other nononcologic diseases [1] . The use of photosensitizing agents
for inactivation of several cancer cells has been widely
studied [2] . Due to their high molar absorption coefficient in the red
part of the spectrum, photostability, and long lifetimes of the
photoexicited triplet states, phthalocyanines (Pcs) are known to be
useful photosensitizers [3, 4] . The aggregation properties of Pcs are
very important for the development of new photosensitizers [5] .
The aim of our ongoing research is to synthesize
water-soluble phthalocyanines to be used as potential PDT agents.
In this work; photophysical, (fluorescence quantum yields and
lifetimes), photochemical (singlet oxygen and photodegradation
quantum yields) and biological properties of water soluble
quarternized metal free, zinc and indium phthalocyanines
including trifluoromethylquinoline substituents on the peripheral
positions are presented.
references:
1. A.C. Tedesco, J.C.G. Rotta, C.N. Lunardi, Curr. Org.
Chem. 7 (2003) 187–196.
2. J. Moan, K. Berg, Photochem. Photobiol. 55 (1992)
931–948.
3. S. Kudrevich, N. Brasseur, C. La Madeline, S. Gilbert,
J. E. van Lier, J. Med. Chem. 40 (1997) 3897–3904.
4. R. Bonnett, Chem. Soc. Rev. 24 (1995) 19–33.
5. K. Tabata, K. Fukushima, K. Oda, I.J. Okura,
J. Porphyrins Phthalocyanines.4 (2000) 278–284.
Keywords: DNA; Singlet oxygen; Phthalocyanines;
Photodynamic theraphy;
4 th EucheMs chemistry congress
P - 0 2 1 7
reverSiBLe PhASe trAnSforMAtion And
MeChAnoChroMiC LuMineSCenCe of zn(ii)-
And Cd(ii)-diPyridyLAMide CoordinAtion
frAMeworKS
B. C. tzenG 1
1 National Chung Cheng University, Chemistry and
Biochemistry, Chiayi, Taiwan
A 1-D double-zigzag framework, {[Zn(paps) (H O) ](ClO ) } 2 2 2 4 2 n
(1)(paps = N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl thioether),
was synthesized by the reaction of Zn(ClO ) with paps. However,
4 2
a similar reaction, except that dry solvents were used instead, led
to the formation of a novel 2-D polyrotaxane framework,
[Zn(paps) (ClO ) ] (2). The above difference relies on the fact
2 4 2 n
that water coordinates to the Zn(II) ion in 1, but ClO 4
- anion
coordination is found in 2. Notably, both structures can be
interconverted by heating and grinding in the presence of
moisture, and such structural transformation can also be proven
experimentally by powder and single-crystal X-ray diffraction
studies. The related papo (papo = N,N'-bis(pyridylcarbonyl)-4,4'diaminodiphenyl
ether) and papc (papc = N,N'-(methylenedi-p-
-phenylene)bispyridine-4-carboxamide) ligands were used to react
with Zn(II) ions as well. When we performed a similar reaction with
dry solvents, except that papo was used instead of paps, the product
mixture contained mononuclear [Zn(papo)(CH OH) ](ClO ) (5)
3 4 4 2
and the polyrotaxane [Zn(papo) (ClO ) ] (4). From the PXRD
2 4 2 n
data, grinding this mixture in the presence of moisture
resulted in the total conversion to the pure double-zigzag
{[Zn(papo) (H O) ](ClO ) } (3) immediately. Upon heating
2 2 2 4 2 n
the double-zigzag 3, the polyrotaxane framework of
[Zn(papo) (ClO ) ] (4) can be recovered. The double-zigzag
2 4 2 n
{[Zn(papc) (H O) ](ClO ) } (6) and polyrotaxane [Zn(papc) (ClO ) ] 2 2 2 4 2 n 2 4 2 n
(7) can be synthesized in a similar reaction. Although heating the
double-zigzag 6 can undergo structural transformation to give the
polyrotaxane 7, grinding its solid samples in the presence of
moisture cannot lead to the formation of the double-zigzag 6.
Significantly, the bright emissions for double-zigzag frameworks
of 1 and 3 and weak ones for polyrotaxane frameworks of 2 and
4, respectively, can also show interesting mechanochromic
luminescence. The related Cd(II)-dipyridylamide coordination
frameworks have been also investigated for the comparison
purpose.
Keywords: phase transformation; mechanochromic
luminescence; coordination frameworks;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc