title: Water coordinated zinc dioxo-chlorin and porphyrin self-assemblies as chlorosomal mimics: variability of supramolecular interactions.
abstract: 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.
authors.affiliation: Max-Planck-Institut für Bioanorganische Chemie, P.O. Box 10 13 65, D-45413 Mülheim a.d. Ruhr, Germany. aldo@chalmers.se
authors.forename: Aldo
authors.initials: A
authors.lastname: Jesorka
authors.forename: Alfred R
authors.initials: AR
authors.lastname: Holzwarth
authors.forename: Andreas
authors.initials: A
authors.lastname: Eichhöfer
authors.forename: Chilla Malla
authors.initials: CM
authors.lastname: Reddy
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Kinoshita
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Tamiaki
authors.forename: Martin
authors.initials: M
authors.lastname: Katterle
authors.forename: Jean-Valère
authors.initials: JV
authors.lastname: Naubron
authors.forename: Teodor Silviu
authors.initials: TS
authors.lastname: Balaban
mesh_terms: D001429:Bacteriochlorophylls / Q000737:chemistry / Q000378:metabolism; D040761:Biomimetic Materials / Q000737:chemistry / Q000378:metabolism; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D008968:Molecular Conformation; D011166:Porphyrins / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D001429:Bacteriochlorophylls; D008665:Metalloporphyrins; D011166:Porphyrins; C558702:zinc chlorin; D014867:Water