| 1. |
- Andreasson, Joakim, 1973, et al.
(författare)
-
Efficient non-radiative deactivation and conformational flexibility of meso-diaryloctaalkylporphyrins in the excited triplet state
- 2000
-
Ingår i: Journal of Physical Chemistry A. - 1089-5639 .- 1520-5215. ; 104:41, s. 9307-9314
-
Tidskriftsartikel (refereegranskat)abstract
- The excited triplet state deactivation of zinc(II) meso-diaryloctaalkylporphyrins (ZnDAOAP) has been studied over a wide temperature range using transient triplet-triplet absorption spectroscopy together with steady-state and time-resolved phosphorescence techniques, The results from transient absorption measurements show that the depopulation of the initially formed triplet state (T-1A state) is unusually fast at temperatures above 150 K. The efficiency of the deactivation originates from a spin allowed transition to a second tripler state (T-1B state), The transformation process T-1A-->T-1B is therefore the dominating deactivation channel of the T-1A state in this temperature range, and direct intersystem crossing T-1A-->S-0 makes negligible contribution. The subsequent ground-state recovery T-1B-->S-0 is also very efficient in comparison to many other porphyrins. Due to the substantial activation energy found for the transformation process, it most likely involves a conformational distortion of the porphyrin macrocycle. At low temperature, however, the relaxation of the T-1A State occurs by direct intersystem crossing to the ground state.
|
|
| 2. |
- Andreasson, Joakim, 1973, et al.
(författare)
-
Photoinduced hole transfer from the triplet state in a porphyrin-based donor-bridge-acceptor system
- 2003
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 107:42, s. 8825-8833
-
Tidskriftsartikel (refereegranskat)abstract
- The triplet excited-state deactivation of a gold porphyrin (AuP) in porphyrin-based donor-bridge-acceptor (D-B-A) systems has been studied. The results from room temperature and 80 K measurements are presented. The primary objectives have been to investigate whether electrons/electron holes or excitation energy could be transferred from (AuP)-Au-3 to the appended zinc porphyrin (ZnP) in the dimers. As the bridging chromophores in our D-B-A systems separate the ZnP and AuP moieties by 19 A edge-to-edge, we do not expect a significant contribution to either electron or energy transfer from a direct (through space) exchange mechanism. This gives us the opportunity to scrutinize how the bridging chromophores influence the transfer reactions. The results show that quenching of (AuP)-Au-3 occurs with high efficiency in the dimers that are connected by fully conjugated bridging chromophores, whereas no quenching is observed when the conjugation of the bridge is broken. We also observed that the decay of (AuP)-Au-3 is complex at temperatures below 110 K. In addition to the two previously published lifetimes on the order of some 10-100 mus, we have found a third lifetime on the nanosecond time scale.
|
|
| 3. |
- Andreasson, Joakim, 1973, et al.
(författare)
-
Temperature and viscosity dependence of the triplet energy transfer process in porphyrin dimers
- 2002
-
Ingår i: Photochemical & Photobiological Sciences. - : Springer Science and Business Media LLC. - 1474-905X .- 1474-9092. ; 1:2, s. 111-119
-
Tidskriftsartikel (refereegranskat)abstract
- The temperature and viscosity dependence of the triplet energy transfer (TET) process in porphyrin dimers has been studied. A zinc porphyrin (donor) and a free base porphyrin (acceptor) are covalently linked together by rigid bridging chromophores at a center-center distance of 25 Angstrom. Due to the large donor-acceptor distance and the weakness of the spin forbidden transitions involved, neither direct (through space) electron exchange nor Coulombic mechanisms are expected to contribute to the observed TET process. The results from transient absorption measurements at temperatures between room temperature and 80 K show that TET occurs with unexpectedly high efficiency in the systems connected by fully conjugated bridges and a pronounced temperature dependence of the process is observed. Comparison of the TET efficiencies in dimers connected by different bridging chromophores correlates well with a transfer reaction governed by a through bond exchange (superexchange) interaction. However, in high viscosity media the TET process is dramatically slowed down. This is attributed to a conformational gating of the TET process where the electronic coupling varies strongly with the relative orientation of the donor and the bridging chromophore. Further, the zinc porphyrin donor offers two distinct donor species, T-1A and T-1B. At room temperature, the TET rate constant of the T-1A Species is about two orders of magnitude larger than for the T-1B species. The dimers studied are well suited model systems for materials where the rate of the transfer reactions can be changed by external stimuli.
|
|
| 4. |
- Andreasson, Joakim, 1973, et al.
(författare)
-
The gold porphyrin first excited singlet state
- 2002
-
Ingår i: Photochemistry and Photobiology. - 0031-8655 .- 1751-1097. ; 76:1, s. 47-50
-
Tidskriftsartikel (refereegranskat)abstract
- Gold porphyrins are often used as electron-accepting chromophores in artificial photosynthetic constructs. Because of the heavy atom effect, the gold porphyrin first-excited singlet state undergoes rapid intersystem crossing to form the triplet state. The lowest triplet state can undergo a reduction by electron donation from a nearby porphyrin or another moiety. In addition, it can be involved in triplet-triplet energy transfer interactions with other chromophores. In contrast, little has been known about the short-lived singlet excited state. In this work, ultrafast time-resolved absorption spectroscopy has been used to investigate the singlet excited state of Au(III) 5,15-bis(3,5-di-t-butylphenyl)-2,8,12,18,-tetraethyl-3,7,13,17-tetrameth ylporphyrin in ethanol solution. The excited singlet state is found to form with the laser pulse and decay with a time constant of 240 fs to give the triplet state. The triplet returns to the ground state with a lifetime of 400 ps. The lifetime of the singlet state is comparable with the time constants for energy and photoinduced electron transfer in some model and natural photosynthetic systems. Thus, it is kinetically competent to take part in such processes in suitably designed supermolecular systems.
|
|
| 5. |
|
|
| 6. |
- Engman, Cecilia, 1974, et al.
(författare)
-
DNA adopts normal B-form upon incorporation of highly fluorescent DNA base analogue tC: NMR structure and UV-Vis spectroscopy characterization
- 2004
-
Ingår i: Nucleic Acids Research. - : Oxford University Press (OUP). - 1362-4962 .- 0305-1048. ; 32:17, s. 5087-95
-
Tidskriftsartikel (refereegranskat)abstract
- The influence of the highly fluorescent tricyclic cytosine base analogue (tC) on duplex DNA conformation is investigated. The duplex properties are characterized by absorbance and circular dichroism (CD) for all combinations of neighbouring bases to tC, and an NMR structure is determined for one tC-containing sequence. For the oligonucleotides with one tC incorporated instead of cytosine, the melting temperature is increased on average by 2.7 degrees C above that for the unmodified ones. CD spectra are practically identical for modified and unmodified sequences, indicating an unperturbed B-DNA conformation. The NMR structure determination of the self-complementary sequence 5'-CTC(tC)ACGTGGAG shows a DNA conformation consistent with B-form for the whole duplex. The root-mean-square distance for the nucleotides of the eight central base pairs between the 10 structures with lowest CYANA target functions and a mean structure is 0.45 +/- 0.17 A. The NMR data confirm correct base pairing for tC by the observation of both intrastrand and interstrand imino proton NOEs. Altogether, this suggests that tC works well as a cytosine analogue, i.e. it is situated in the base stack, forming hydrogen bonds with G in the complementary strand, without distorting the DNA backbone conformation. This first example of an artificial, highly fluorescent DNA base that does not perturb the DNA conformation could have valuable applications for the study of the structure and dynamics of nucleic acid systems.
|
|
| 7. |
- Kilså, Kristine, 1972, et al.
(författare)
-
Bridge-dependent electron transfer in porphyrin-based donor-bridge-acceptor systems
- 2001
-
Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 123:13, s. 3069-3080
-
Tidskriftsartikel (refereegranskat)abstract
- Photoinduced electron transfer in donor-bridge-acceptor systems with zinc porphyrin (or its pyridine complex) as the donor and gold(III) porphyrin as the acceptor has been studied. The porphyrin moieties were covalently linked with geometrically similar bridging chromophores which vary only in electronic structure. Three of the bridges are fully conjugated pi -systems and in a fourth, the conjugation is broken. For systems with this bridge, the quenching rate of the singlet excited state of the donor was independent of solvent and corresponded to the rate of singlet energy transfer expected for a Forster mechanism. In contrast, systems with a rr-conjugated bridging chromophore show a solvent-dependent quenching rate that suggests electron transfer in the Marcus normal region. This is supported by picosecond transient absorption measurements, which showed formation of the zinc porphyrin radical cation only in systems with pi -conjugated bridging chromophores. On the basis of the Marcus and Rehm-Weller equations, an electronic coupling of 5-20 cm(-1) between the donor and acceptor is estimated for these systems. The largest coupling is found for the systems with the smallest energy gap between the donor and bridge singlet excited states. This is in good agreement with the coupling calculated with quantum mechanical methods, as is the prediction of an almost zero coupling in the systems with a nonconjugated bridging chromophore.
|
|
| 8. |
- Kilså, Kristine, 1972, et al.
(författare)
-
Control of electron transfer in supramolecular systems
- 2001
-
Ingår i: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy. - 1386-1425. ; 57:11, s. 2213-2227
-
Tidskriftsartikel (refereegranskat)abstract
- The fluorescence quantum yield of zinc porphyrin (ZnP) covalently linked to 9,10-bis(phenylethynyl)anthracene (AB) is strongly dependent upon the solvent properties. The bichromophoric system ZnP-AB exhibits 'normal' zinc porphyrin fluorescence in solvents that cannot coordinate to the central zinc atom. In contrast, if a Lewis base, such as pyridine, is added to a sufficiently polar solvent, the fluorescence is significantly quenched. Picosecond transient absorption measurements, in conjunction with fluorescence quenching and cyclic voltammetric measurements, suggest that the quenching mechanism is intramolecular electron transfer from ZnP to AB. The charge separated state, ZnP.+-AB(.-), has a lifetime of not more than 220 ps before recombining. If a secondary electron acceptor, iron(III) porphyrin (FeP), is covalently connected to the AB unit, a second electron transfer from AB(.-) to FeP occurs and the charge separated state, ZnP.+-AB-FeP.-, has a lifetime of at least 5 ns. This demonstrates that electron transfer might be sensitively tuned (switched on) by specific solvent effects. (C) 2001 Elsevier Science BN. All rights reserved.
|
|
| 9. |
- Kilså, Kristine, et al.
(författare)
-
Enhanced Intersystem Crossing in Donor/Acceptor Systems Based on Zinc/Iron or Free-Base/Iron Porphyrins
- 2001
-
Ingår i: Chemistry, A European Journal. - 1521-3765 .- 0947-6539. ; 7:10, s. 2122-33
-
Tidskriftsartikel (refereegranskat)abstract
- The deactivation pathways of the singlet excited state of a series of zinc or free-base donor porphyrins covalently linked by a bridge to a paramagnetic iron(iii) chloride porphyrin acceptor have been studied. These donor-bridge-acceptor systems all share a similar geometry (25 Å donor-acceptor center-to-center distance), but the bridges vary in electronic structure. In previously reported investigations of zinc/iron porphyrin systems, the fluorescence quenching of the donor has predominantly been assigned to electron transfer. However, for the porphyrin systems studied in this paper, we show that the dominant deactivation channels are enhanced intersystem crossing and singlet energy transfer. In both series, the intersystem crossing rate (S1T1) of the donor moiety is almost doubled in the presence of a paramagnetic high-spin metal-porphyrin acceptor. The significant spectral overlap of the donor fluorescence and acceptor absorption in both series allows for efficient singlet energy transfer (Förster mechanism). Furthermore, the bridging chromophores mediate energy transfer and the enhancement is inversely dependent upon the energy gap between the donor and bridge excited states. Although Marcus theory predicts thermodynamically favorable electron transfer to occur in the systems investigated, the quenching rate constants were found to be independent of solvent polarity, and no charge-separated state could be detected, indicating very small electronic coupling for electron transfer.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2111/2001/f2779_s.pdf or from the author. 1H NMR spectra of FeP, FeP-OB, FeP-BB, FeP-NB, FeP-AB, ZnP-OB-FeP, ZnP-BB-FeP, ZnP-NB-FeP, and ZnP-AB-FeP.
|
|
| 10. |
- Kyrychenko, A., et al.
(författare)
-
Conformer-dependent electronic coupling for long-range triplet energy transfer in donor-bridge-acceptor porphyrin dimers
- 2002
-
Ingår i: Chemical Physics Letters. - 0009-2614. ; 366:3-4, s. 291-299
-
Tidskriftsartikel (refereegranskat)abstract
- The electronic coupling for triplet energy transfer is calculated by time-dependent density functional theory (TDDFT) for a set of tri-chromophoric systems based on a zinc(II) porphyrin donor and the corresponding free base acceptor covalently connected by different hydrocarbon bridging chromophores. The calculated electronic coupling, for systems with identical donor acceptor distances, is sensitive to the bridge electronic structure and shows a significant dependence for the bridge and donor-bridge conformations. The computational results compare quantitatively to measurements of triplet energy transfer rates in the corresponding donor-bridge-acceptor systems. (C) 2002 Elsevier Science B.V. All rights reserved.
|
|
