Abstract
Bis-MPA dendron-coated free-base tetraphenylporphyrin and zinc-tetraphenyl-porphyrin (TPPH2 and TPPZn) were studied in comparison with simple porphyrins (H2P, ZnP) by theoretical simulation of their infrared, Raman and electronic absorption spectra, as well as fluorescense emission. Infrared and fluorescence spectra of the dendrimers were measured and interpreted along with time-resolved measurements of the fluorescence. The 0–1 emission band of the dendron substituted TPPZn was found to experience a “heavy substitution”-effect. The 0–1 vibronic emission signal is associated with a longer decay time (approx. 7 - 8 ns) than the 0-0 emission (approx. 1 - 1.5 ns). The former contributed with more relative emission yield for larger dendron substituents, in agreement with the appearance of steady-state emission spectra showing increased contribution from the 0–1 vibronic fluorescence band at 650 nm. No such substitution effect was observed in the electronic or vibrational spectra of the substituted free-base variant, TPPH2. Vibration spectra of the parent porphyrins (H2P, ZnP, TPPH2 and TPPZn) were calculated by density functional theory (DFT) using the B3LYP/6-31G** approximation and a detailed analysis of the most active vibration modes was made based on both literature and our own experimental data. Based on the results of theoretical calculations the wide vibronic bands in the visible region were assigned. The vibronic structure also gave a qualitative interpretation of bands in the electronic absorption spectra as well as in fluorescence emission depending on the size of dendrimer substitution. From the results of time-dependent DFT calculations it is suggested that the TPPZn-cored dendrimers indicate strong vibronic interaction and increased Jahn-Teller distortion of the prophyrin core for larger dendrimer generations. Specifically, this leads to the entirely different behaviour of the emission spectra upon substitution of the TPPH2 and TPPZn variants, which was also experimentally observed. Since TPPH2 is originally of lower symmetry the specific distortion upon dendron substitution is not expected to the same extent, which also was in agreement with the experimental findings.
Highlights
Porphyrins are important chromophores that play a crucial role in a number of biological processes such as photosynthesis, dioxygen transport and activation, and photodynamic cancer therapy [1,2,3,4]
The first excited singlet state of the H2P molecule is 1B3u and the same "effective" symmetry can be used for the tetraphenyl derivative, since the electronic excitation is located mostly in the porphyrin ring
The synthesis and basic properties of dendrimers based on free-base tetraphenylporphyrin and zinctetraphenylporphyrin (TPPH2 and TPPZn) were reported some years ago [29]
Summary
Porphyrins are important chromophores that play a crucial role in a number of biological processes such as photosynthesis, dioxygen transport and activation, and photodynamic cancer therapy [1,2,3,4]. Porphyrin photochemistry provides insight into the dynamics of related biomolecules, such as the photosynthetic reaction centers in purple bacteria and green plants and heme-based metalloproteins such as hemoglobin and myoglobin. Much of this work has recently been focused on free-base and metalloporphyrin assemblies for light-harvesting purposes, porphyrin containing mimics of the photosynthetic reaction center, and electronic devices. The last decades have witnessed a vast number of experimental studies of porphyrins which have yielded very useful information about their electronic structure and optical spectra (see for example, [1,2,3,5,6,7]), but it has not always been possible to provide a well reasoned explanation of the results obtained [8,9,10,11,12].
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