Platinum(II) diimine dithiolates. New solution luminescent complexes

Zuleta, Juan A.; Burberry, Mitch S.; Eisenberg, Richard

doi:10.1016/0010-8545(90)80079-9

Cited by 169 publications

(126 citation statements)

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“…Platinum diimine dithiolate complexes (PtN 2 S 2 ) such as 1 constitute another class of charge transfer chromophores that are solution luminescent and undergo electron transfer quenching of both oxidative and reductive types (42)(43)(44)(45)(46)(47)(48). The excited state energies of these complexes are significantly lower than those of the Ru(bpy), Ir(ppy), and Pt(terpyridyl) complexes mentioned above and have an excited state that has been described as having both MLCT and ligand-to-ligand charge transfer (LLCT) character.…”

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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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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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“…where dpphen = 4,7-diphenyl-1,10-phenanthroline, ecda = 1-(ethoxycarbonyl)-1-cyanoethylene-2,2 0 -dithiolate (4)) 5 are luminescent in solution at room temperature though the emission quantum yields for the complexes except for complex 3 are not so high. The number of highly luminescent platinum(II) complexes has been increasing recently due to an interest in developing phosphorescent materials for organic lightemitting devices (OLED), and for cyclometalated platinum(II) complexes such as [Pt(46dfppy)(acac)] (H46dfppy = 2-(4 0 ,6 0 -difluorophenyl)pyridine, Hacac = acetylacetone, 5) and platinum(II) complexes with acetylide ligands (e.g.…”

Section: Structural Classification Of Luminescent Platinum(ii) Complexesmentioning

confidence: 99%

Luminescent Platinum Complexes Having Sensing Functionalities

Kato¹

2007

Bulletin of the Chemical Society of Japan

208

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Square-planar platinum(II) complexes often exhibit intense color and luminescence when they are stacked via selfassembly or bridging by ligands. The origin of the color and luminescence are the metal-metal electronic interactions, and thus, remarkable changes in color (i.e., chromism) are expected by controlling the PtÁÁÁPt interactions. The molecular arrangement of the assembled complex systems is sensitive to environmental factors such as temperature, pressure, solvent, and vapor. This account focuses on the sensing functionalities of luminescent platinum(II) complexes with 2,2 0 -bipyridine or its derivatives toward their environment. Especially, luminescence changes that are induced by the vapor molecules will be examined from the viewpoint of chemical sensing. The vapochromic behavior and structural aspects of the mononuclear and dinuclear platinum(II) complexes are discussed.

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“…[m] [33] Pt(phen)(i-mnt) [a] PhNO 2 423 23641 -1.22r -1.73r +1.15ir [33] Pt(phen)(qdt) [a] DMSO 458 21834 -1.06r -+0.95ir [25,26] Pt(phen)(tdt) [a] CH 2 Cl 2 583 17153 -1.319r r +0.376qr…”

Section: Explanation and Physical Basismentioning

confidence: 99%

“…[m] [22,24,41] Pt(phen)(dpdt) [e] CH 2 Cl 2 620 16129 --+0.30r [35] Pt(phen)(bbdt) [e] CH 2 Cl 2 627 15949 --+0.24r [35] Pt(bipym)(mnt) [e] DMSO 493 20284 +1.32ir [44] Pt(bipym)(dmit) [e] DMSO 560 17857 +0.80ir [44] Pt(BABA)(mnt) [33] Pt(dmbpy)(tdt) [a] CH 2 Cl 2 563 17762 -1.371r r +0.390ir [22,24,41] Pt(dpbpy)(mnt) [a] CH 2 Cl 2 513 19493 -1.18r -1.68r +0.70 [33] Pt(dpbpy)(i-mnt) [a] CH 2 Cl 2 448 22321 -1.11r -1.71r +0.72 [33] Pt(dbbpy)(tbcda) [a] CH 2 Cl 2 437 22883 -1.302r r +0.963ir [24] Pt(dbbpy)(cpdt) [a] CH 2 Cl 2 434 23041 -1.274r r +0.957ir [24] Pt(dbbpy)(endt) [a] CH 2 Cl 2 480 20833 -1.484r r +0.431ir [24] Pt(dbbpy)(dmqdt) [a] CH 2 Cl 2 481 20790 -1.334r r +0.814ir [24] Pt(dbbpy)(mnt) [a] CH 2 Cl 2 497 20121 -1.266r r +0.944ir [24] Pt(dbbpy)(tdt) [a] CH 2 Cl 2 563 17762 -1.398r r +0.389ir [24] Pt(dbbpy)(S-4-py) 2…”

Section: Explanation and Physical Basismentioning

confidence: 99%

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Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

Makedonas

Mitsopoulou

2007

Eur J Inorg Chem

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In order to quantify the contribution of mainly, but not only, diimine ligands to the electronic properties of the corresponding complexes, two novel indices, namely modified electronic parameters (ModEP) and electrophilicity, ω, are introduced and discussed in this report. First, we introduce the concept of ModEP, a novel scale relating to the electronic properties of diimine ligands. Mainly on the basis of wellcharacterized M(diimine)(dithiolato) complexes (M = Pt, Pd, or Ni), we derive the contribution of the diimine ligand to the reduction potentials of the complexes, and incorporating its contribution to the main charge-transfer band of the UV/Vis spectra, we obtain our ModEP values. The applicability of the introduced scale to several other classes of diimine compounds (W, Re, and Ru) is then tested. The performance of our scale in predicting the values of the reduction potentials and the position of the charge-transfer bands is very satisfactory. With this approach, some interesting aspects of ligand

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Platinum(II) diimine dithiolates. New solution luminescent complexes

Cited by 169 publications

References 36 publications

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

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

Luminescent Platinum Complexes Having Sensing Functionalities

Introduction of Modified Electronic Parameters – Searching for a Unified Ligand Properties Scale through the Electrophilicity Index Concept

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