1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section UV/Vis spectroscopy was performed on a Shimadzu UV-3102 PC UV/Vis/NIR Scanning Spectrophotometer or a SPECORD® S 600 spectrophotometer (Analytik Jena AG). Mass spectrometry (MS) was done on either a MIRCOMASS ZABSPEC spectrometer (FAB + mode, 3-nitro benzylic alcohol as matrix) or on a Shimadzu AXIMA Confidence spectrometer (MALDI- TOF, linear mode). Elemental Analysis (EA) was done on a CE INSTRUMENTS EA 1110 CHNS. Calculations were performed by utilization of ACCELRYS MATERIALS STUDIO® 99 or SPARTAN® 130 on the semiempirical PM3 or PM6 level. Methods providing results achieved in cooperation with the groups of C. MARIAN (University of Düsseldorf) or of G. BRINGMANN (University of Würzburg) are referred to as references in the text. Ground state absorption spectroscopy was performed on a commercial Shimadzu UV- 2501PC spectrophotometer. Steady-state fluorescence spectroscopy was conducted in 1 cm×1 cm quartz cells by utilization of the combination of a cw-Xenon lamp (XBO 150) and a monochromator (Lot- Oriel, bandwidth 10 nm) for excitation and a polychromator with a cooled CCD matrix as detector system (Lot-Oriel, Instaspec IV). Decay associated fluorescence spectroscopy (DAFS): Those spectra were acquired using the time correlated single photon counting (TCSPC) technique in combination with scanning of the detection wavelength in an experimental setup known to literature. 106 A pulsed, frequency doubled, linear polarized radiation of a Nd:VO4 laser (Cougar, Time Bandwidth Products, wavelength: 532 nm, pulse width: 12 ps, repetition rate: 60 MHz) was used directly for excitation of the samples or to synchronously pump a dye laser (Model 599, Coherent) tunable in the range of 610 to 670 nm. Fluorescence was detected under a "magic" angle relative to excitation. Data were analyzed by a homemade program in applying a variable projection algorithm 107b to the global fitting problem. The Nelder-Mead simplex algorithm 107a was used for optimization of the nonlinear parameters, and the support plane approach 107c to compute error estimates of the decay times. Model functions were sums of up to three exponentials convoluted by the instrument response function (42 ps as measured with Ludox) including a time shift. Decay times and time shift were linked through all measurements of one scan sampled every 2.5 nm. 138
Experimental Section 6 Picosecond transient absorption spectroscopy (ps-TAS): Firstly, a white light continuum was generated as a test beam within a cell containing D2O/H2O using intense 25 ps pulses from a Nd 3+ :YAG laser (PL 2143A, Ekspla) at 1064 nm. Before passing through the sample, the continuum radiation was split to obtain a reference spectrum. The transmitted as well as the reference beam were focused into two optical fibers and recorded simultaneously at different traces on a CCD matrix (Lot-Oriel, Instaspec IV). As excitation beam, tunable radiation from an OPO/OPG (Ekspla PG 401/SH, tuning range 200-2300 nm) pumped by the 3 rd harmonic of the same laser was used. The mechanical delay line allowed the measurement of light-induced changes of the absorption spectrum at different delays of up to 15 ns after excitation. The analysis of experimental data was performed using the compensation method. 109 Photosensitized steady-state singlet oxygen luminescence was measured at 1270 nm upon excitation of the samples at 515 nm by a cw Yb:YAG laser (Versadisk, ELS) equipped with a frequency doubling unit. The corresponding set up for the detection of the luminescence signal is reported in literature. 111b Cyclic voltammetry measurements were performed on an Autolab Instrument with PGSTAT 30 in a three electrodes arrangement (Deutsche Metrohm GmbH & Co. KG): measuring electrode: gold disc electrode (0.07 cm 2 ); counter electrode: Pt wire; reference electrode: Ag/AgCl (3 M NaCl) at constantly 25°C in CH2Cl2 solution (electrochemistry grade). Scan rates: ν = 50 mV·s -1 . Supporting electrolyte: n-Bu4NPF6 at c = 0.1 M. Potentials given vs. ferrocene with E(Fc/Fc + ) = +0.53 V as internal standard. Enantiomeric resolution by HPLC: Analytical resolutions were performed on Jasco HPLC systems (pump PU1580, gradient unit LG-980-025 or LG-2080-04, degasser DG-2080-53 or DG-2080-54, UV detector MD-2010Plus or Erma Cr. Inc. Erc-7215) equipped with Chirex (S)- Val or Lux Cellulose-1 columns (4.6x250 mm; 5μm), both PHENOMENEX, as chiral phases. LC-CD coupling: Online CD spectra were recorded at room temperature using a Jasco 715 spectropolarimeter (scanning rate: 500 nm/min, bandwidth: 0.5 nm, response time: 0.5 s, number of accumulations: 5). 139
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Semi-Natural and Synthetic Chiral C
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Die vorliegende Arbeit entstand in
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Table of Contents 1 Introduction 1
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n J j-coupling (constant) with n in
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1 Introduction characteristics. For
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1 Introduction 1.1 Porphyrins - A G
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1 Introduction Especially interesti
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1 Introduction 8 [H] 4 + 4 O H O H
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1 Introduction complexes are usuall
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1 Introduction transitions as it is
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1 Introduction 1.2 Photodynamic The
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1 Introduction Certainly, Photofrin
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1 Introduction intact membranes bei
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1 Introduction components, the limi
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2 State of The Art & Aims They were
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2 State of The Art & Aims 2.2 Aim o
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3 Discussion and Results encapsulat
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3 Discussion and Results diastereot
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3 Discussion and Results 30 E ½ Re
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3 Discussion and Results irradiatio
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3 Discussion and Results 34 R 1 O N
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3 Discussion and Results 3.2.2.1.2
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3 Discussion and Results Table 4. S
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3 Discussion and Results 3.2.2.2 FR
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3 Discussion and Results 3.2.2.3 Ac
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3 Discussion and Results 3.2.3.1 IR
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3 Discussion and Results 3.2.3.2 NM
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3 Discussion and Results 3.2.3.3 Va
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3 Discussion and Results 3.2.3.3.2
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3 Discussion and Results Obviously,
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3 Discussion and Results Like Figur
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3 Discussion and Results utilizatio
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3 Discussion and Results has been d
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3 Discussion and Results other TPP
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3 Discussion and Results (being sup
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3 Discussion and Results other band
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3 Discussion and Results Table 10.
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3 Discussion and Results voltammogr
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3 Discussion and Results 3.2.5 Inhe
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3 Discussion and Results effects 12
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3 Discussion and Results 74 Δθ [m
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3 Discussion and Results 3.2.6.2 10
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3 Discussion and Results vibration
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3 Discussion and Results 3.2.6.4 Sy
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3 Discussion and Results cyanomethy
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3 Discussion and Results 3.2.6.5 Co
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3 Discussion and Results phenyl sub
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6 Experimental Section broad signal
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7 References 16 H. Fischer, K. Zeil
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7 References 57 S. Schwartz, K. Abs
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7 References 89 (a) R. C. Fuson, J.
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7 References 131 (a) J. Perdew, Phy
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S. Jasinski, N. Jux, “Investigati
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Ein großer Dank gilt auch den Ange
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Cirruculum vitae Stefan Jasinski Ge
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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