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Nanomolecular singlet oxygen photosensitizers based on hemiquinonoid-resorcinarenes, the fuchsonarenes.

ABSTRACT: Singlet oxygen sensitization involving a class of hemiquinonoid-substituted resorcinarenes prepared from the corresponding 3,5-di-t-butyl-4-hydroxyphenyl-substituted resorcinarenes is reported. Based on variation in the molecular structures, quantum yields comparable with that of the well-known photosensitizing compound meso-tetraphenylporphyrin were obtained for the octabenzyloxy-substituted double hemiquinonoid resorcinarene reported herein. The following classes of compounds were studied: benzyloxy-substituted resorcinarenes, acetyloxy-substituted resorcinarenes and acetyloxy-substituted pyrogallarenes. Single crystal X-ray crystallographic analyses revealed structural variations in the compounds with conformation (i.e., rctt, rccc, rcct) having some influence on the identity of hemiquinonoid product available. Multiplicity of hemiquinonoid group affects singlet oxygen quantum yield with those doubly substituted being more active than those containing a single hemiquinone. Compounds reported here lacking hemiquinonoid groups are inactive as photosensitizers. The term 'fuchsonarene' (fuchson + arene of resorcinarene) is proposed for use to classify the compounds.

SUBMITTER: Payne DT

PROVIDER: S-EPMC7069522 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Nanomolecular singlet oxygen photosensitizers based on hemiquinonoid-resorcinarenes, the fuchsonarenes.

Payne Daniel T DT Webre Whitney A WA Gobeze Habtom B HB Seetharaman Sairaman S Matsushita Yoshitaka Y Karr Paul A PA Chahal Mandeep K MK Labuta Jan J Jevasuwan Wipakorn W Fukata Naoki N Fossey John S JS Ariga Katsuhiko K D'Souza Francis F Hill Jonathan P JP

Chemical science 20200218 10

Singlet oxygen sensitization involving a class of hemiquinonoid-substituted resorcinarenes prepared from the corresponding 3,5-di-<i>t</i>-butyl-4-hydroxyphenyl-substituted resorcinarenes is reported. Based on variation in the molecular structures, quantum yields comparable with that of the well-known photosensitizing compound <i>meso</i>-tetraphenylporphyrin were obtained for the octabenzyloxy-substituted double hemiquinonoid resorcinarene reported herein. The following classes of compounds wer ...[more]

PMID: 32206265

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Project description:Heavy-atom-free sensitizers forming long-living triplet excited states via the spin-orbit charge transfer intersystem crossing (SOCT-ISC) process have recently attracted attention due to their potential to replace costly transition metal complexes in photonic applications. The efficiency of SOCT-ISC in BODIPY donor-acceptor dyads, so far the most thoroughly investigated class of such sensitizers, can be finely tuned by structural modification. However, predicting the triplet state yields and reactive oxygen species (ROS) generation quantum yields for such compounds in a particular solvent is still very challenging due to a lack of established quantitative structure-property relationship (QSPR) models. In this work, the available data on singlet oxygen generation quantum yields (ΦΔ ) for a dataset containing >70 heavy-atom-free BODIPY in three different solvents (toluene, acetonitrile, and tetrahydrofuran) were analyzed. In order to build reliable QSPR model, a series of new BODIPYs were synthesized that bear different electron donating aryl groups in the meso position, their optical and structural properties were studied along with the solvent dependence of singlet oxygen generation, which confirmed the formation of triplet states via the SOCT-ISC mechanism. For the combined dataset of BODIPY structures, a total of more than 5000 quantum-chemical descriptors was calculated including quantum-chemical descriptors using density functional theory (DFT), namely M06-2X functional. QSPR models predicting ΦΔ values were developed using multiple linear regression (MLR), which perform significantly better than other machine learning methods and show sufficient statistical parameters (R=0.88-0.91 and q2 =0.62-0.69) for all three solvents. A small root mean squared error of 8.2 % was obtained for ΦΔ values predicted using MLR model in toluene. As a result, we proved that QSPR and machine learning techniques can be useful for predicting ΦΔ values in different media and virtual screening of new heavy-atom-free BODIPYs with improved photosensitizing ability.

Dataset Information

Nanomolecular singlet oxygen photosensitizers based on hemiquinonoid-resorcinarenes, the fuchsonarenes.

Publications

Nanomolecular singlet oxygen photosensitizers based on hemiquinonoid-resorcinarenes, the fuchsonarenes.

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