Water coordinated zinc dioxo-chlorin and porphyrin self-assemblies as chlorosomal mimics: Variability of supramolecular interactions
Journal article, 2012
Semisynthetic zinc chlorins are shown for the first time to self-assemble in the absence of an intrinsic hydroxy group, which is always present in the chlorosomal bacteriochlorophylls (BChl's) c, d and e. Instead, the presently studied compounds have carbonyl groups. These cannot function as hydrogen bond donating groups. However due to interspacing water molecules bound to the zinc ion, double hydrogen bonding can occur to adjacent tetrapyrrolic macrocycles equipped with carbonyl recognition groups. Solution studies comprising UV-Vis absorption, electronic circular dichroism (ECD) and FT-IR show that different aggregates are formed in hydrated solvents in comparison to dry nonpolar solvents. Single crystal X-ray studies show variable supramolecular interactions either with interspacing water molecules coordinating the Zn ion within a porphyrin or with the 17 2 carbonyl group of a chlorin ligating the Zn ion. Our findings have implications for a minimalistic design of self-assembling chromophores, which can act as efficient light-harvesting units.
Author
Aldo Jesorka
Chemistry and biochemistry - Phd students
A. R. Holzwarth
Max-Planck-Institut für Bioanorganische Chemie
Andreas Eichöfer
Karlsruhe Institute of Technology (KIT)
Chilla Malla Reddy
Indian Institute of Science
Karlsruhe Institute of Technology (KIT)
Y. Kinoshita
Ritsumeikan University
Hitoshi Tamiaki
Ritsumeikan University
M. Katterle
Max-Planck-Institut für Bioanorganische Chemie
Jean-Valere Naubron
Aix Marseille University
Teodor Silviu Balaban
Aix Marseille University
Karlsruhe Institute of Technology (KIT)
Max-Planck-Institut für Bioanorganische Chemie
Photochemical and Photobiological Sciences
1474-905X (ISSN) 1474-9092 (eISSN)
Vol. 11 6 1069-1080Subject Categories
Inorganic Chemistry
Physical Chemistry
Theoretical Chemistry
DOI
10.1039/c2pp25016k
PubMed
22522667