Synthesis of Zinc 3-Hydroxymethyl-porphyrins Possessing Carbonyl Groups at the 13- and/or 15-Positions for Models of Self-Aggregative Chlorophylls in Green Photosynthetic Bacteria

Abstract

Zinc 3-hydroxymethyl-protopyropheophorbide-d derivatives 1, 2, and 3 possessing carbonyl group(s) at the 13/15-, 13-, and 15-positions, respectively, and 4 lacking the C=O group were prepared from naturally occurring chlorophyll-a. Zinc porphyrins 1 and 2 possessing the 13-C=O self-aggregated in an aqueous micellar solution, similarly to the self-aggregates of BChls-c/d/e in the main light-harvesting antenna systems of green photosynthetic bacteria, whereas 3 and 4 lacking the 13-C=O failed to make such well-ordered aggregates. These results indicated that both the presence of the C=O group and its situation at the 13-position were preferable for formation of the well-ordered J-aggregates.

Unique photophysical properties of chlorophyll derivatives linked with CO 2 -reducing moiety along the Qy axis

“…Chlorophyll derivatives Chl-H, Chl(deoxo)-H, and ZnChl(deoxo)-H and a rhenium complex Rebpy-OH were prepared according to previously reported procedures [23][24][25][26][27][28]. Covalently linked chlorophyllrhenium bipyridine complexes Chl(deoxo)-Rebpy and ZnChl (deoxo)-Rebpy were synthesized by the esterification of dicarboxylic acid Rebpy-OH with alcohols Chl(deoxo)-H and ZnChl(deoxo)-H, respectively (see below and Scheme 1) [23,25,29].…”

Solvent-dependent moulding of porphyrin-based nanostructures: solid state, solution and on surface self-assembly

“…a have been self-assembled in chlorosomal-type aggregates (26)(27)(28)(29)(30)(31). Additionally, synthetic porphyrin analogues revealed to be good models for mimicking chlorosomes by employing the same self-assembly recognition groups that are found in BChl's (32)(33)(34).…”

“…The self-assembly algorithm for this family of (semi)synthetic derivatives is made of three key points: a central metal ion, a hydroxy group and a keto function. Meticulous tailoring of these three groups enabled a given self-organisation with coordination to the central metal atom with the hydroxy of another molecule as main contact that, through a lateral hydrogen-bond with a keto group of a third molecule, organises the stacks together with π-π interactions (26)(27)(28)(29)(30)(31)(32)(33)(34).…”

Photophysical Properties and Electronic Structure of Chlorin-Imides: Bridging the Gap between Chlorins and Bacteriochlorins

“…41,46,47 Others contain substituents in the isocyclic ring. 23,[37][38][39][40]54,59,61,63,65 The m a j o r i t y a r e d e r i v e d f r o m n a t u r a l c h l o r ophylls, 37,44,52,59,63,64,66,67,70 particularly chlorophyll a, whereas others have been prepared by derivatization of synthetic porphyrins, particularly 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP). [38][39][40][41][42][43][45][46][47]61,66 Examples of substituents include formylvinyl, dicyanovinyl, and quinonyl units.…”

“…The Q y absorption band of synthetic zinc and free base chlorins (including 13 1 -oxophorbines) bearing simple substituents resides in the range 598–687 nm, , whereas the chlorin-imides absorb in a longer wavelength region, from 660 to 714 nm. A number of chlorins without imide groups have been prepared that also have long-wavelength absorption ( vide infra ). ,− However, the chlorin-imides are distinctive as synthetically accessible and tailorable chromophores that fill the gap in the spectral progression of synthetic free base or zinc chlorins lacking imides (598–687 nm) to chlorin-imides (660–714 nm) and on to synthetic bacteriochlorins and bacteriochlorin-imides , (from 709 to >800 nm).…”