BODIPY and dipyrrin as unexpected robust anchoring groups on TiO2 nanoparticles

Jayworth, Josephine A.; Capobianco, Matt D.; Liu, Han-Yu; Decavoli, Cristina; Crabtree, Robert H.; Brudvig, Gary W.

doi:10.1039/d2dt02116a

Title: BODIPY and dipyrrin as unexpected robust anchoring groups on TiO₂ nanoparticles

Journal Article · Tue Aug 30 00:00:00 EDT 2022 · Dalton Transactions

DOI:https://doi.org/10.1039/d2dt02116a· OSTI ID:1978891

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Yale Univ., New Haven, CT (United States); Yale Univ., West Haven, CT (United States). Energy Sciences Institute
Yale Univ., New Haven, CT (United States); Yale Univ., West Haven, CT (United States). Energy Sciences Institute; Univ. di Milano (Italy)

Covalent attachment of molecules to metal oxide surfaces typically demands the presence of an anchoring group that in turn requires synthetic steps to introduce. BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) chromophores have long been used in dye-sensitized solar cells, but carboxylic acid groups typically had to be installed to act as surface anchors. We now find that even without the introduction of such anchors, the unmodified BODIPY can bind to TiO₂ surfaces via its BF₂ group through boron–oxygen surface bonds. Dipyrrin, the parent molecule of BODIPY, is also capable of binding directly to TiO₂ surfaces, likely through its chelating nitrogen atoms. These binding modes prove to be even more robust than that of an installed carboxylate and offer a new way to attach molecular complexes to surfaces for (photo)catalytic applications since, once bound, we show that surface bound BODIPY and dipyrrin derivatives exhibit ultrafast photoinjection of electrons into the conduction band of TiO₂.

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Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE

Grant/Contract Number:: FG02-07ER15909

OSTI ID:: 1978891

Alternate ID(s):: OSTI ID: 1885627

Journal Information:: Dalton Transactions, Vol. 51, Issue 37; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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