Pentacene- and BODIPY-Containing trans-Bis(ethynyl)bis(phosphine)platinum(II) Organometallic Polymers: A DFT Point of View

Bonnot, Antoine; Harvey, Pierre D.

doi:10.1007/s10904-016-0405-8

Cited by 6 publications

(2 citation statements)

References 75 publications

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“…For EtBPtB and EtNIPtB-2 , the respective acetylide ligand is also rotated to orthogonality with the platinum coordination plane, whereas it is almost coplanar with the platinum coordination plane (and, hence, in an orthogonal arrangement with respect to the plane of the BODIPY ligand) in EtNIPtB-1 . This finding already indicates that electronic π interactions between the two different trans-disposed dye ligands across the platinum ion are at best weak in the solid state, although they have been implicated on several occasions in explaining the electronic and photophysical properties of platinum diphosphinebis(acetylide) oligomers and polymers. ,− ,,, Such a lack of electronic interactions in complexes with two different dye ligands is not without precedence , and results from the inherently nonidentical energies of the corresponding dye-based MOs. This is also in accordance with the results of our quantum-chemical calculations on the full models of complexes EtBPtB and EtNIPtB-2 , where, despite the coplanarity of the dye ligands, all crucial MOs are largely localized at the BODIPY or acetylide ligand with only modest delocalization between them (vide infra).…”

Section: Resultsmentioning

confidence: 99%

Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis–Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes

et al. 2016

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We report on the platinum complexes trans-Pt(BODIPY)(8-ethynyl-BODIPY)(PEt) (EtBPtB) and trans-Pt(BODIPY)(4-ethynyl-1,8-naphthalimide)(PR) (R = Et, EtNIPtB-1; R = Ph, EtNIPtB-2), which all contain two different dye ligands that are connected to the platinum atom by a direct σ bond. The molecular structures of all complexes were established by X-ray crystallography and show that the different dye ligands are in either a coplanar or an orthogonal arrangement. π-stacking and several CH···F and short CH···π interactions involving protons at the phosphine substituents lead to interesting packing motifs in the crystal. The complexes feature several strong absorptions (ε = 3.2 × 10-5.5 × 10 M cm) that cover the regime from 350 to 480 nm (EtNIPtB-1 and EtNIPtB-2) or from 350 to 580 nm (EtBPtB). Besides the typical absorption bands of both kinds of attached dyes, they also feature an intense band near 400-420 nm, which is assigned by time-dependent density functional theory calculations to a higher-energy transition within the ethynyl-BODIPY (EtB) ligand or to charge transfer between the BODIPY (B) and naphthalimide (NI) chromophores. All complexes show dual fluorescence and phosphorescence emission from either the B (EtNIPtB-1 and EtNIPtB-2) or EtB (EtBPtB) ligand with a maximum phosphorescence quantum yield of 41% for EtNIPtB-1. The latter seems to be the highest reported value for room temperature phosphorescence from a BODIPY dye. The complete quenching of the emission from the chromophore absorbing at the higher energy and the appearance of the corresponding absorption bands in the fluorescence and phosphorescence excitation spectra indicate complete and rapid energy transfer to the chromophore with the lower-energy excited state, i.e., EtNI → B in EtNIPtB-1 and EtNIPtB-2 and B → EtB in EtBPtB. The latter process was further investigated by transient absorption spectroscopy, indicating that energy transfer is complete within 0.6 ns. EtNIPtB-1 catalyzes the photooxidation of 1,5-dihydroxynaphthalene with photogenerated O to Juglone at a much faster rate than methylene blue but with only modest quantum yields of 37% and with the onset of photodegradation after 60 min.

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Section: Resultsmentioning

confidence: 99%

Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis–Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes

et al. 2016

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“…11,12 Since then, various polymers containing trans-Pt(CuC-Ar) 2 (PR 3 ) 2 moieties have been reported, mainly focusing on photoelectrical properties tunable by arylene units, including thiophene, carbazole and boron-dipyrromethene. [13][14][15] In contrast, there are only a few reports concerning polymers containing cis-Pt(CuC-Ar) 2 (PR 3 ) 2 moieties, 16 presumably because of rapid geometric isomerization of the Pt center from cis to trans during dehydrochlorination coupling.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of geometry-controlled platinum-containing polymers bearing optically active bidentate phosphine ligands

Horiuchi,

Makino,

Sano

et al. 2024

Polym. Chem.

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Organometallic and Coordination Polymers, and Linear and Star Oligomers Using the trans-Pt(PR3)2(C≡C)2 Linker

Harvey

2017

J Inorg Organomet Polym

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Pentacene- and BODIPY-Containing trans-Bis(ethynyl)bis(phosphine)platinum(II) Organometallic Polymers: A DFT Point of View

Cited by 6 publications

References 75 publications

Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis–Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes

Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis–Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes

Synthesis of geometry-controlled platinum-containing polymers bearing optically active bidentate phosphine ligands

Organometallic and Coordination Polymers, and Linear and Star Oligomers Using the trans-Pt(PR3)2(C≡C)2 Linker

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