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Nucleophilic addition of phosphorus(iii) derivatives to squaraines: colorimetric detection of transition metal-mediated or thermal reversion.

ABSTRACT: Nucleophilic addition of phosphorus(iii) agents to the electrophilic core of intensely colored squaraine dyes gives a bleached zwitterionic adduct in good to excellent yields (up to 99%) at room temperature. The process can be reversed by adding specific transition metal complexes with high phosphorous(iii) affinity.

SUBMITTER: Bacher EP

PROVIDER: S-EPMC6857784 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Nucleophilic addition of phosphorus(iii) derivatives to squaraines: colorimetric detection of transition metal-mediated or thermal reversion.

Bacher Emily P EP Lepore Antonio J AJ Pena-Romero Deisy D Smith Bradley D BD Ashfeld Brandon L BL

Chemical communications (Cambridge, England) 20190227 22

Nucleophilic addition of phosphorus(iii) agents to the electrophilic core of intensely colored squaraine dyes gives a bleached zwitterionic adduct in good to excellent yields (up to 99%) at room temperature. The process can be reversed by adding specific transition metal complexes with high phosphorous(iii) affinity. ...[more]

PMID: 30810572

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Project description:Meso tetraarylporphyrinato gold(iii) cations bearing different substituents at the aryl substituents (COOMe, COOH, NO2, NH2, NHAc, H, O n Bu, CF3) were prepared and characterised. Their reversible one-electron reductions were studied by (spectro)electrochemical means as well as by selective chemical one-electron reduction using cobaltocene. The preferred location of the spin density, namely gold centred or porphyrin centred, was probed by electron paramagnetic resonance spectroscopy (g values, 197Au hyperfine coupling) as well as by density functional theory calculations (spin densities). In all cases studied experimentally and theoretically, the gold(ii) valence isomer (5d9 electron configuration) is preferred over the porphyrin π radical anion. In the hexafluorophosphate salt of the nitro derivative a further nitro π radical anion valence isomeric species is significantly populated. In the presence of chloride ions this nitro π radical anion/AuII valence isomeric equilibrium evolves towards the porphyrin π radical anion. The electronic structures of the nitro π radical and the AuII σ radical valence isomers (5d x2-y2 orbital) could be calculated by DFT methods. The electron transfer pathway between the nitro π radical anion and the AuII valence isomer is well described by the location of the hexfluorophosphate counterion, the Au-N distances (corresponding to the totally symmetric stretching vibration), the symmetric stretching mode of the NO2 substituent and a meso-nitrophenyl rotation. The specific geometric and electronic properties of the favoured gold(ii) σ radical valence isomer, namely counterion dislocation and σ symmetry of the redox orbital, might stabilise charge-shifted states [(gold(ii) porphyrin)-donor˙+] by retarding the back electron transfer to give the ground state (gold(iii) porphyrin)-donor. This will guide the design of (photo-induced) electron transfer pathways with tetraarylporphyrinato gold(iii) complexes as electron acceptors.

Dataset Information

Nucleophilic addition of phosphorus(iii) derivatives to squaraines: colorimetric detection of transition metal-mediated or thermal reversion.

Publications

Nucleophilic addition of phosphorus(iii) derivatives to squaraines: colorimetric detection of transition metal-mediated or thermal reversion.

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