Synthesis, Photophysics, Electrochemistry and Electrogenerated Chemiluminescence of PEG-Modified BODIPY Dyes in Organic and Aqueous Solutions

Nepomnyashchii, Alexander B.; Pistner, Allen J.; Bard, Allen J.; Rosenthal, Joel

doi:10.1021/jp312166w

Cited by 54 publications

(43 citation statements)

References 57 publications

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“…The inability of these systems to harvest solar energy at wavelengths longer than ~450 nm is a critical impediment to the use of sunlight to drive CO 2 reduction, since the solar power spectrum is most intense from approximately 425 – 600 nm. Since BODIPY 47 – 51 and other polypyrrole derivatives 52–55 can absorb light throughout the visible region we rationalized that [Re(BB2)(CO) 3 Cl] might support an improved photocatalysis with CO 2 using sunlight, as compared to fac -Re I (CO) 3 frameworks lacking indacene units. 56 …”

Section: Resultsmentioning

confidence: 91%

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

et al. 2014

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The reduction of carbon dioxide to chemical fuels such as carbon monoxide is an important challenge in the field of renewable energy conversion. Given the thermodynamic stability of carbon dioxide, it is difficult to efficiently activate this substrate in a selective fashion and the development of new electrocatalysts for CO2 reduction is of prime importance. To this end, we have prepared and studied a new fac-ReI(CO)3 complex supported by a bipyridine ligand containing ancillary BODIPY moieties ([Re(BB2)(CO)3Cl]). Voltammetry experiments revealed that this system displays a rich redox chemistry under N2, as [Re(BB2)(CO)3Cl] can be reduced by up to four electrons at modest potentials. These redox events have been characterized as the ReI/0 couple, and three ligand based reductions – two of which are localized on the BODIPY units. The ability of the BB2 ligand to serve as a non-innocent redox reservoir is manifest in an enhanced electrocatalysis with CO2 as compared to an unsubstituted Re-bipyridine complex lacking BODIPY units ([Re(bpy)(CO)3Cl]). The second order rate constant for reduction of CO2 by [Re(BB2)(CO)3Cl] was measured to be k = 3400 M−1s−1 at an applied potential of −2.0 V versus SCE, which is roughly three times greater than the corresponding unsubstituted Re-bipyridine homologue. Photophysical and photochemical studies were also carried out to determine if [Re(BB2)(CO)3Cl] was a competent platform for CO2 reduction using visible light. These experiments showed that this complex supports unusual excited state dynamics that precludes efficient CO2 reduction and are distinct from those that are typically observed for fac-ReI(CO)3 complexes.

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Section: Resultsmentioning

confidence: 91%

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

et al. 2014

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“…A silver wire was used as the quasi-reference electrode and calibrated against ferrocene. All redox potentials are reported vs. the Fc/Fc + couple that has a value of 0.40 V vs. SCE with SCE = 0.24 relative to NHE (50,(53)(54)(55)(56)(57). The cyclic voltammograms of the Pt(diimine)(bdt) complexes 1(bpyC) and 1(bpyP) each exhibit two reversible reductions in the ranges between −1.39 V to −1.41 V and −1.9 V to −2.03 V, as well as two irreversible oxidations in the range 0.04-0.54 V (Fig.…”

Section: Resultsmentioning

confidence: 99%

Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes

Zheng

Sabatini

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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New dyads consisting of a strongly absorbing Bodipy (dipyrromethene-BF 2 ) dye and a platinum diimine dithiolate (PtN 2 S 2 ) charge transfer (CT) chromophore have been synthesized and studied in the context of the light-driven generation of H 2 from aqueous protons. In these dyads, the Bodipy dye is bonded directly to the benzenedithiolate ligand of the PtN 2 S 2 CT chromophore. Each of the new dyads contains either a bipyridine (bpy) or phenanthroline (phen) diimine with an attached functional group that is used for binding directly to TiO 2 nanoparticles, allowing rapid electron photoinjection into the semiconductor. The absorption spectra and cyclic voltammograms of the dyads show that the spectroscopic and electrochemical properties of the dyads are the sum of the individual chromophores (Bodipy and the PtN 2 S 2 moieties), indicating little electronic coupling between them. Connection to TiO 2 nanoparticles is carried out by sonication leading to in situ attachment to TiO 2 without prior hydrolysis of the ester linking groups to acids. For H 2 generation studies, the TiO 2 particles are platinized (Pt-TiO 2 ) so that the light absorber (the dyad), the electron conduit (TiO 2 ), and the catalyst (attached colloidal Pt) are fully integrated. It is found that upon 530 nm irradiation in a H 2 O solution (pH 4) with ascorbic acid as an electron donor, the dyad linked to Pt-TiO 2 via a phosphonate or carboxylate attachment shows excellent light-driven H 2 production with substantial longevity, in which one particular dyad [4(bpyP)] exhibits the highest activity, generating ∼40,000 turnover numbers of H 2 over 12 d (with respect to dye).photochemistry | solar energy conversion | hydrogen | spectroscopy | synthesis W ater splitting into hydrogen and oxygen is the key energystoring reaction of artificial photosynthesis (AP) and one of the most promising long-term strategies for carbon-free energy on a potentially global scale (1). As a redox reaction, water splitting has been studied primarily in terms of its two halfreactions, the reduction of aqueous protons to H 2 and the oxidation of water to O 2 (2-13). Whereas some of these studies date back more than 30 y (14-22), recent progress on each halfreaction has been notable, particularly with regard to catalyst development and mechanistic understanding of each transformation (6,(23)(24)(25)(26)(27)(28)(29). In this paper, we focus on efforts dealing with the lightdriven generation of H 2 , which in its simplest form requires a light absorber or photosensitizer (PS) for electron-hole creation, a means or pathway for charge separation and electron transfer, an aqueous proton source, a catalyst for collecting electrons and protons and promoting their conversion to H 2 , and an ultimate source of electrons in the form of an electron donor.Dating from the earliest work on the light-driven generation of H 2 , the photosensitizer has most often been a Ru(II) complex with 2,2′-bipyridine (bpy) and/or related heterocyclic ligands having a long-lived triplet metal-to-ligand ...

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“…Analytical thin-layer chromatography (TLC) was performed on precoated glass plates and visualized by UV or by staining with KMnO 4 . 4-Hydroxymethyl-4’-methyl-2,2’-bipyridine ( 2 ), 38 4-Bromomethyl-4’-methyl-2,2’-bipyridine ( 3 ), 38 and BODIPY derivatives ( 9 and 10 ) 39 were prepared as previously described in literature.…”

Section: Methodsmentioning

confidence: 99%

Photocatalytic Conversion of CO₂ to CO Using Rhenium Bipyridine Platforms Containing Ancillary Phenyl or BODIPY Moieties

et al. 2013

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Harnessing of solar energy to drive the reduction of carbon dioxide to fuels requires the development of efficient catalysts that absorb sunlight. In this work, we detail the synthesis, electrochemistry and photophysical properties of a set of homologous fac-ReI(CO)3 complexes containing either an ancillary phenyl (8) or BODIPY (12) substituent. These studies demonstrate that both the electronic properties of the rhenium center and BODIPY chromophore are maintained for these complexes. Photolysis studies demonstrate that both assemblies 8 and 12 are competent catalysts for the photochemical reduction of CO2 to CO in DMF using triethanolamine (TEOA) as a sacrificial reductant. Both compounds 8 and 12 display TOFs for photocatalytic CO production upon irradiation with light (λex ≥ 400 nm) of ~5 hr−1 with TON values of approximately 20. Although structural and photophysical measurements demonstrate that electronic coupling between the BODIPY and fac-ReI(CO)3 units is limited for complex 12, this work clearly shows that the photoactive BODIPY moiety is tolerated during catalysis and does not interfere with the observed photochemistry. When taken together, these results provide a clear roadmap for the development of advanced rhenium bipyridine complexes bearing ancillary BODIPY groups for the efficient photocatalytic reduction of CO2 using visible light.

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Synthesis, Photophysics, Electrochemistry and Electrogenerated Chemiluminescence of PEG-Modified BODIPY Dyes in Organic and Aqueous Solutions

Cited by 54 publications

References 57 publications

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes

Photocatalytic Conversion of CO₂ to CO Using Rhenium Bipyridine Platforms Containing Ancillary Phenyl or BODIPY Moieties

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Synthesis, Photophysics, Electrochemistry and Electrogenerated Chemiluminescence of PEG-Modified BODIPY Dyes in Organic and Aqueous Solutions

Cited by 54 publications

References 57 publications

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes

Photocatalytic Conversion of CO2 to CO Using Rhenium Bipyridine Platforms Containing Ancillary Phenyl or BODIPY Moieties

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Photocatalytic Conversion of CO₂ to CO Using Rhenium Bipyridine Platforms Containing Ancillary Phenyl or BODIPY Moieties