Crystal structure of <i>cis</i>-7,8-dihydroxy-5,10,15,20-tetraphenylchlorin and its zinc(II)–ethylenediamine complex

Chaudhri, Nivedita; Brückner, Christian; Zeller, Mat­thias

doi:10.1107/s2056989022002729

Cited by 2 publications

(1 citation statement)

References 41 publications

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“…Because F x BC (presumably isomerized from F x ChPh) is present in the quenched photolysis mixtures, we study its impact on CO 2 RR with an independently synthesized F 20 BC. The crystal structure of F 20 BC shows two characteristic C–C single bonds in the pyrrole ring, which exhibit similar distances compared with reported Ch and bacteriochlorins (BC) compounds (Supplementary Table 10 ) 57 , 58 . Under the same conditions, the system with F 20 BC exhibits a much lower initial TOF (60 h −1 ) than that with F 20 Ch (Supplementary Fig.…”

Section: Resultssupporting

confidence: 63%

Fluorinated chlorin chromophores for red-light-driven CO2 reduction

Yang,

Yuan,

Guo

et al. 2024

Nat Commun

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The utilization of low-energy photons in light-driven reactions is an effective strategy for improving the efficiency of solar energy conversion. In nature, photosynthetic organisms use chlorophylls to harvest the red portion of sunlight, which ultimately drives the reduction of CO2. However, a molecular system that mimics such function is extremely rare in non-noble-metal catalysis. Here we report a series of synthetic fluorinated chlorins as biomimetic chromophores for CO2 reduction, which catalytically produces CO under both 630 nm and 730 nm light irradiation, with turnover numbers of 1790 and 510, respectively. Under appropriate conditions, the system lasts over 240 h and stays active under 1% concentration of CO2. Mechanistic studies reveal that chlorin and chlorinphlorin are two key intermediates in red-light-driven CO2 reduction, while corresponding porphyrin and bacteriochlorin are much less active forms of chromophores.

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Section: Resultssupporting

confidence: 63%

Fluorinated chlorin chromophores for red-light-driven CO2 reduction

Yang,

Yuan,

Guo

et al. 2024

Nat Commun

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Osmium ester-hinged chlorin dimers

Chaudhri

Dorazio

Samankumara

et al. 2023

J. Porphyrins Phthalocyanines

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A bis(dihydroxychlorin) osmate ester is formed as a side product in the osmylation of meso-tetraphenylporphyrin. The product can also be formed in good yield along well-known reaction pathways of osmate esters by treatment of the monomeric chlorin diol osmate ester bispyridine complex with acid. The dimer was spectroscopically characterized. The free base dimer can be metalated with zinc(II). The bis([dihydroxychlorinato]zinc) osmate ester dimer was spectroscopically and structurally characterized, showing its clamshell architecture with a 42[Formula: see text] angle between the mean planes of the two metallochlorin chromophores and a 9.11 Å zinc-to-zinc separation. Upon reaction with dimethylaminopyridine (DMAP), the clamshell structure pivots around the osmium center and arranges the two chromophores, each zinc center coordinated to DMAP, in maximum separation from each other, as shown by structural analysis. Preliminary 1H NMR titration data are presented that show the bis-zinc clamshell structure to form a 1:1 supramolecular complex with diethylenetriamine (DETA), expressing a three-point recognition motive: the terminal amine functionalities coordinate to the zinc ions in each half-shell, thus bridging both chromophores, and the central amine functionality was deduced to be H-bonded to the osmium oxo group pointing toward the inside of the host. The UV-vis spectroscopic response upon DETA binding shows greater complexity in the interaction at higher ligand:host ratios, suggesting multiple binding modes. A similarly complex binding situation is also observed for the interactions of the chlorin osmate ester monomer with DETA.

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Crystal structure of cis-7,8-dihydroxy-5,10,15,20-tetraphenylchlorin and its zinc(II)–ethylenediamine complex

Cited by 2 publications

References 41 publications

Fluorinated chlorin chromophores for red-light-driven CO2 reduction

Fluorinated chlorin chromophores for red-light-driven CO2 reduction

Osmium ester-hinged chlorin dimers

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