Solvatochromic and emissive properties of pt(II) complexes with 1,1- and 1,2-ditholates

Zuleta, Juan A.; Bevilacqua, Joanne M.; Eisenberg, Richard

doi:10.1016/0010-8545(91)84029-5

Cited by 86 publications

(89 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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.…”

mentioning

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.

Self Cite

View full text Add to dashboard Cite

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 ...

show abstract

mentioning

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.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Without further purification, the precipitate was then treated with 3 molar equivalents of acetylacetone and 10 equivalents of Na 2 CO 3 in 2-ethoxyethanol (8 mL) at 100°C under nitrogen for 16 h. After the removal of all volatile components, the compound was purified by column chromatography on silica using CH 2 Cl 2 /hexane mixture as the eluent to afford the desired products. (4) 13.1924 (7) 15.1757 (7) 11.6935 (6) 10.895(1) b (Å) 11.4511 (9) 11.537(1) 11.6085 (7) 11.9666 (6) 12.8628 (6) 8.6213 (4) 13.886(2) c (Å) 13.557 (1) 13.693 (2) 14.9566 (9) 32.939 (2) 17.5829 (8) …”

Section: General Procedures For the Synthesis Of Cyclometalated Platimentioning

confidence: 98%

“…The strong ligand field associated with such ligands raises the energy of the metal d-d states, withdrawing their deactivating effect. Among them, Pt(II) complexes incorporating pyridine ligands such as bipyridine [11][12][13][14][15][16][17][18][19][20][21][22][23] and terpyridine [24] derivatives have attracted a great deal of interest as luminescent dyes for OLED applications since they often exhibit high phosphorescence quantum yields. On the other hand, several cyclometalated homo-or heteroleptic Pt(II) complexes based on 2-phenylpyridine (ppy) and analogues have been reported in the literature [25][26][27].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

Wong

Yao

et al. 2009

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…These relations are given by Equations (28), (29), (30), and (31). The majority of the entries are for phosphane ligands, because TEP and CEP have been derived for these types of compounds.…”

Section: Electrophilicity Index ω -Application To Diimine Ligandsmentioning

confidence: 99%

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

Makedonas

Mitsopoulou

2007

Eur J Inorg Chem

View full text Add to dashboard Cite

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

show abstract

Solvatochromic and emissive properties of pt(II) complexes with 1,1- and 1,2-ditholates

Cited by 86 publications

References 26 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

Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

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

Contact Info

Product

Resources

About