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Abstract
Spectroscopic properties of H2 TPP porphyrin and Tb(III)TPP(acac) in solid and methanolic solutions have been compared. Emission from
the S1 singlet state of Tb(III)TPP(acac) have been recorded at 296 and 77 K. Spectroscopic investigations of new types of porphyrins soluble
in organic solvents (e.g. methanol), PP(AA)2 , and porphyrins soluble in water, PP(AA)2 (Arg)2 (where AA, alanine or serine; Arg, arginine),
are presented. Interaction of PP(AA)2 with lanthanide ions (Yb(III), Eu(III)) has been studied. It has been found that the lanthanide (III) ions
decrease efficiency of the porphyrin emission. For the alanine derivative, the stronger losses are caused by the Eu(III) ions as compared to the
Yb(III) ions. On the other hand, the emission quenching by both lanthanide ions is similar in the case of the serine derivative. Influence of the
Pr(III) and Eu(III) ions on the PP(AA)2 (Arg)2 emission has also been investigated. An unexpected increase of the porphyrin emission intensity
has been observed in solution for the lowest concentration of Pr(III) added, whereas the Eu(III) ions quench the emission in the full range
of its concentration. The observed phenomena are analyzed, and the mechanisms of the excited-state dynamics in which the f-excited states
take part in the porphyrin emission quenching are considered. It has been found that the lanthanide ions influence the absorption spectrum as
well as the relative intensities of the respective bands in the emission spectra. The luminescence intensities of these porphyrins as a function
of pH, the concentration and the type of the porphyrine substituent have been analyzed. Significant influence of the above factors on the
emission properties of the porphyrins has been found and discussed. Efficiency of the emission has been determined for these M-porphyrin
systems in comparison to the free porphyrins in methanol solutions. The observed effects can be explained by formation of polymeric chains
and decrease of face-to-face agglomeration that leads to effective quenching.
2004 Published by Elsevier B.V.
Keywords: Photophysics of the Ln(III):porphyrin systems; New types of porphyrins; Water-soluble porphyrins; UVVis spectroscopy; Lanthanide(III) ions
1. Introduction
Porphyrins attract large attention because of their role in
the human body, ability to accumulate in many kinds of cancer cells, as well as magnetic and optical properties. These
features make them useful in cancer medicine and photodynamic therapy [13]. The porphyrins are molecules, whose
physicochemical properties can be easily adjusted by modifications of the electronic distribution on the aromatic ring
through peripheral substitutions that plays an important role
in many biological systems and in photochemistry [46].
For example, the existence of such complexes is crucial for
Corresponding author. Tel.: +48-71-3204-300;
fax: +48-71-3282-348.
E-mail address: jl@wchuwr.chem.uni.wroc.pl (J. Legendziewicz).
397
NH
N
HN
2. Experimental
(a)
O
R =
CH3
OH
HO
NH
Ser
R
CH3
NH
or
O
H3C
R =
OH
HN
NH
CH3
H3C
Ala
CH2
CH2
(b)
O
R =
CH3
OH
HO
NH
Ser
R
CH3
NH
or
O
R =
H3C
OH
HN
NH
CH3
H3C
Ala
O
O
CH2
CH2
CH2
CH2
COO H
C NH3 +
COO + H3N
H
C
CH2
CH2
CH2
CH2
CH2
CH2
NH
NH
NH2
NH
H2N
NH
(c)
Fig. 1. Structural formulas of (a) H2 TPP, (b) PP(AA)2 and (c)
PP(AA)2 (Arg)2 ; AA, Ser and Ala.
398
2.0
Soret band
414,6
B(0,0)
(II)
1.5
Absorbance
(I)
250
Q band
1.0
300
350
400
Qy(1,0)
450
500
Qy(0,0) Qx(1,0)
415,6
Q(1,0)
478,6
550
550,9
508,2
600,8
600
650
700
Qx(0,0)
660
Q(0,0)
(II)
589,6
0.5
(I)
395,2
500
550
600
650
700
(II)
(I)
0.0
350
400
450
500
550
600
650
700
Wavelength [nm]
Fig. 2. Absorption spectra of TbTPP(acac) (I) and H2 TPP (II) in nujol.
10
Soret band
411
em
= 650 nm
B(0,0)
6
Q band
393
Q (1,0)
Q (0,0)
2
514
551
430
597
0
350
400
450
500
550
Wavelength [nm]
Fig. 3. Excitation spectrum of TbTPP(acac) in CH3 OH, c = 105 M.
600
651,5
(I)
(II)
650,8
399
exc = 400 nm
Q(0,0)
Q(0,0)
Q(0,1)
Q(0,1)
713,8
713,5
605
600
650
700
750
600
Wavelength [nm]
650
700
750
Wavelength [nm]
Fig. 4. Emission spectra of TbTPP(acac) (I) and H2 TPP (II) in CH3 OH at 293 K, c = 105 M.
of the extra band at 605 nm for (I). At 77 K (Fig. 5), the compounds still exhibit emission from the S1 singlet state of the
porphyrin, independently of the excitation wavelength. This
implies that at 77 K, the rate of the S2 S1 internal conversion can be reached, involving the 5 D4 level of the Tb(III)
ion as it can be seen from energy-level diagram. Also, dissociation can be efficient enough to give efficient emission
of the free porphyrin. Moreover, we do not consider the role
of the -diketonate singlet and triplet states in the photoluminescence of the Tb(III) complex because of the large
distance between them and the porphyrine ring. Presumably,
(I)
1 exc = 413.5 nm
644,95
(II)
2 exc = 383 nm
1 exc = 400 nm
646,5
2 exc = 383 nm
Q(0,0)
Q(0,0)
1
1
Q(0,1)
2
Q(0,1)
711
713,2
0
550
600
650
Wavelength [nm]
700
750
550
600
650
700
Wavelength [nm]
Fig. 5. Emission spectra of TbTPP(acac) (I) and H2 TPP (II) in CH3 OH at 77 K, c = 105 M.
750
400
1 PP(Ala) c = 6.1*10
Q(0,0)
2 PP(Ser) c = 5.64*10 M
3 PP(Ala) : Yb (1:1) c = 6.1*10 M
Q(0,0)
625
2, 3
exc = 400 nm
exc = 400 nm
624,4
Q(0,1)
Q(0,1)
689,5
4
579,4
2
5, 6
646,6
550
600
650
700
750
550
600
Wavelength [nm]
650
700
750
Wavelength [nm]
Fig. 6. Emission spectra of the (a) PP(Ser)2 :Ln(III) and PP(Ala)2 :Ln(III) after 12 h in methanol; (b) emission spectra of the PP(Ala)2 :Ln(III).
1 PP2ml
2 PP2ml +0.2mlPrCl3
578,8
578,8
3 PP2ml +0.4mlEuCl3
4 PP2ml +0.6mlPrCl3
1 PP2ml
2 PP2ml +0.2mlEuCl3
(b)
3 PP2ml +0.4mlPrCl3
4 PP2ml +0.6mlEuCl3
5 PP2ml +0.8mlPrCl3
5 PP2ml +0.8mlEuCl3
6 PP2ml +1.0mlPrCl3
6 PP2ml +1.0mlEuCl3
7 PP2ml +1.2mlPrCl3
7 PP2ml +1.2mlEuCl3
Q(0,0)
Q(0,0)
2
2
3
623,4
623,4
Q(0,1)
2
Q(0,1)
678
678
6, 7
5, 6, 7
0
550
600
650
Wavelength [nm]
700
750
550
600
650
700
750
Wavelength [nm]
Fig. 7. Influence of the (a) Pr(III) and (b) Eu(III) ions concentration in the aqueous solution on emission intensity of PP(Ser)2 (Arg)2 .
-3
(a)
623,5
2
Q(0,0)
1 c = 10 M pH = 3.62
-4
2 c = 10 M pH = 4.37
-5
3 c = 10 M pH = 7.71
-6
4 c = 10 M pH = 8.49
30000
porphyrin
Eu(III)
D4
S2
25000
-1
P1
P0
20000
S1
15000
D1
5
D0
D2
B (Soret)
band
S1 emission
Q band
10000
5000
S0
H4
F0
F6
the porphyrins (see Scheme 1), and for this reason, their
role in mediation of the S2 S1 internal conversion should
be considered. First of all, the role of the mediating metal
ion excited states could be different for different ions. Furthermore, the fd transition energy level of the Pr(III) ion,
which is located above the S2 singlet state of the porphyrin
can feed energy to the porphyrin more efficiently at lower
concentrations of the metal ions. At the higher Pr(III) ion
concentrations, we have to consider the dimerization and
agglomeration processes causing quenching of the emission
by possible energy migration through the porphyrin rings.
-3
(b)
408,3
Soret band
B(0,0)
1 c = 10 M pH = 3.62
-4
2 c = 10 M pH = 4.37
-5
3 c = 10 M pH = 7.71
-6
4 c = 10 M pH = 8.49
em = 622 nm
Q band
508,2
544,5 568,8
405,3
621,7
4
1
700
583,5
650
D4
S2 emission
622
Wavelength [nm]
D3
P2
Q(0,1)
600
582,6
550
Tb(III)
exc = 400 nm
Pr(III)
Energy [cm ]
dependent (see Fig. 6). Directly after addition of the lanthanide ions, the emission is analogously quenched, but after
some time, Eu(III) causes higher decrease of the emission
intensity. Subtle differences in the emission can be caused
by different energies of the excited states of the ions and also
by different positions of their CT states. It is worth noting
that no emission was detected from the lanthanide(III) ions.
We have also examined influence of addition of the Pr(III)
and Eu(III) ions on spectroscopic properties of the porphyrin
derivatives possessing arginine as a peripheral substituent
(PP(Ser)2 (Arg)2 , PP(Ala)2 (Arg)2 ) in aqueous solutions.
Fig. 7 shows the S1 emission spectra for PP(Ser)2 (Arg)2
before and after addition of the lanthanide(III) ions. It
should be noted that the band centered at 580 nm exceeds
in intensity the Q(0,0) band, whereas their spectral positions
remain unaffected as compared to the spectrum of the free
porphyrin. It leads to the conclusion that the second substituent of the porphyrin can influence only the intensity of
the bands [22].
As it can be seen, the emission intensity of the porphyrin
exhibits strong dependence on concentration of the lanthanide ions. It increases as the concentration of the Pr(III)
ions increases, reaches maximum, and then decreases (see
Fig. 7a). However, addition of the Eu(III) ions causes immediate decrease of the emission intensity (see Fig. 7b).
Apparently, presence of the Pr(III) and Eu(III) ions in the
solutions influences the S1 porphyrin emission intensity,
which was reported for the first time by us [16]. The question arises why that influence is different for the different
Ln(III) ions (i.e. Pr(III) and Eu(III)).
The 3 P- and 5 D-excited state manifolds of Pr(III) and
Eu(III) are located between the S2 and S1 singlet states of
401
750 300
350
400
450
500
550
Wavelength [nm]
Fig. 8. (a) Emission and (b) excitation spectra of PP(Ala)2 (Arg)2 in the function of concentration.
600
402
-3
(a)
1 c = 10 M pH = 3.46
-4
2 c = 10 M pH = 4.26
-5
3 c = 10 M pH = 7.03
-6
4 c = 10 M pH = 7.25
619,6
Q(0,0)
-3
(b)
1 c = 10 M pH = 3.46
-4
2 c = 10 M pH = 4.26
-5
3 c = 10 M pH = 7.03
-6
4 c = 10 M pH = 7.25
402,3
Soret band
B(0,0)
em = 622 nm
exc = 400 nm
Q band
Q(0,1)
507,3
543,6
567
680,2
412,2
2
326,4
623,2
378,6
2
578,2
684,1
619,6 4
1
550
600
650
700
750 300
350
Wavelength [nm]
400
450
500
550
600
Wavelength [nm]
Fig. 9. (a) Emission and (b) excitation spectra of PP(Ser)2 (Arg)2 in the function of concentration.
As the concentration of the metal ions in the solutions increases, the latter processes start to dominate and the emission intensity decreases.
The above-mentioned facts suggest that the lanthanide
ions may play other roles in the energy dissipation than only
the direct participation in the S2 S1 internal conversion.
Most probably their role, besides the energy transfer from
the fd energy level to the S2 singlet state, might be related
to changes in the organization of the species in the solution.
1 pH = 0.20
2 pH = 1.50
3 pH = 3.71
4 pH = 6.60
5 pH = 8.49
6 pH = 10.66
7 pH = 11.80
(a)
7
Q(0,0)
Another factor influencing absorption and emission spectra of porphyrins is pH. Recently, Dargiewicz et al. [23]
showed the relation between pH and changes in the absorption spectra of porphyrines in different media (water,
alcohol, silica sol-gel). The authors suggest the potential
applications of films (obtained by the dip-coating method)
containing cationic water-soluble porphyrins as the pH
sensors. In our investigations, we have examined the influence of pH on the emission spectra of PP(Ala)2 (Arg)2
(b)
1 pH = 0.20
2 pH = 1.50
3 pH = 3.71
4 pH = 6.60
5 pH = 8.49
6 pH = 10.66
7 pH = 11.80
Soret band
B(0,0)
em = 622 nm
exc = 400 nm
Q(0,1)
Q band
6
43
550
600
3
4
650
Wavelength [nm]
700
750 300
350
400
450
500
550
Wavelength [nm]
Fig. 10. (a) Emission and (b) excitation spectra of PP(Ala)2 (Arg)2 in the function of pH, c = 106 M.
600
(a)
1 pH = 0.30
2 pH = 2.10
3 pH = 3.60
4 pH = 6.80
5 pH = 7.25
6 pH = 10.66
7 pH = 12.00
Q(0,0)
403
1 pH = 0.30
2 pH = 2.10
3 pH = 3.60
4 pH = 6.80
5 pH = 7.25
6 pH = 10.66
7 pH = 12.00
(b)
1
Soret band
B(0,0)
exc = 400 nm
em = 622 nm
Q(0,1)
Q band
550
600
650
750 300
700
350
400
450
500
550
600
Wavelength [nm]
Wavelength [nm]
Fig. 11. (a) Emission and (b) excitation spectra of PP(Ser)2 (Arg)2 in the function of pH, c = 106 M.
(b)
Integrated intensity
(a)
pH
10
12
10
12
pH
Fig. 12. Integrated intensity of the emission vs. pH for (a) PP(Ala)2 (Arg)2 and (b) PP(Ser)2 (Arg)2 .
404
(1)
H3 P+ H2 P + H+
(2)
H2 P HP + H+
(3)
HP P2 + H+
(4)
4. Summary
1. Absorption spectra of solid TbTPP(acac) and H2 TPP are
comparable with the excitation spectra of these compounds in alcoholic solution, which confirms their compositions.
2. The change of the concentration of the free porphyrin
strongly affects the emission spectrum as a result of a
different degree of the agglomeration and concentration
quenching.
3. The emission intensity of the porphyrin depends on the
Pr(III) ion concentrations in the solutions. It increases as
the concentration of the Pr(III) ions increases, reaches a
maximum, and then decreases.
4. The efficiencies of the luminescence in methanol for
the amino acid derivatives of the porphyrins have been
determined. The efficiencies decrease from PP(Ala)2 to
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