Synthesis and characterisation of new acetylide-functionalised oligothiophenes and their dinuclear platinum complexes

Lewis, Jack; Long, Nicholas J.; Raithby, Paul R.; Shields, Gregory P.; Wong, Wai Yeung; Younus, Muhammad

doi:10.1039/a704708h

Cited by 112 publications

(104 citation statements)

References 23 publications

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“…Irie has previously reported that in solution, diA C H T U N G T R E N N U N G (thienyl)cyclopentenes typically exist as a mixture of parallel (C m -symmetric) and antiparallel (C 2 -symmetric) conformers. [7a, 16] The relative simplicity of the 19 F NMR spectrum of 1 o results from interconversion between the parallel and antiparallel conformers occurring rapidly on the NMR timescale. This exchange is in contrast to systems with substituents at the 4-position of the thiophene rings, the spectra of which typically exhibit separate signals for both conformers.…”

Section: Resultsmentioning

confidence: 99%

Highly Efficient Visible‐Light Driven Photochromism: Developments towards a Solid‐State Molecular Switch Operating through a Triplet‐Sensitised Pathway

Brayshaw

Schiffers

Stevenson

et al. 2011

Chemistry A European J

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We introduce a new highly efficient photochromic organometallic dithienylethene (DTE) complex, the first instance of a DTE core symmetrically modified by two Pt(II) chromophores [Pt(PEt(3))(2)(C≡C)(DTE)(C≡C)Pt(PEt(3))(2)Ph] (1), which undergoes ring-closure when activated by visible light in solvents of different polarity, in thin films and even in the solid state. Complex 1 has been synthesised and fully photophysically characterised by (resonance) Raman and transient absorption spectroscopy complemented by calculations. The ring-closing photoconversion in a single crystal of 1 has been followed by X-ray crystallography. This process occurs with the extremely high yield of 80%--considerably outperforming the other DTE derivatives. Remarkably, the photocyclisation of 1 occurs even under visible light (>400 nm), which is not absorbed by the non-metallated DTE core HC≡C(DTE)C≡CH (2) itself. This unusual behaviour and the high photocyclisation yields in solution are attributed to the presence of a heavy atom in 1 that enables a triplet-sensitised photocyclisation pathway, elucidated by transient absorption spectroscopy and DFT calculations. The results of resonance Raman investigation confirm the involvement of the alkynyl unit in the frontier orbitals of both closed and open forms of 1 in the photocyclisation process. The changes in the Raman spectra upon cyclisation have permitted the identification of Raman marker bands, which include the acetylide stretching vibration. Importantly, these bands occur in the spectral region unobstructed by other vibrations and can be used for non-destructive monitoring of photocyclisation/photoreversion processes and for optical readout in this type of efficiently photochromic thermally stable systems. This study indicates a strategy for generating efficient solid-state photoswitches in which modification of the Pt(II) units has the potential to tune absorption properties and hence operational wavelength across the visible range.

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Section: Resultsmentioning

confidence: 99%

Highly Efficient Visible‐Light Driven Photochromism: Developments towards a Solid‐State Molecular Switch Operating through a Triplet‐Sensitised Pathway

Brayshaw

Schiffers

Stevenson

et al. 2011

Chemistry A European J

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“…4) and 2094 to 2085 cm -1 for 4 which is the characteristics of Pt(II)-poly-yne polymers. This may be attributed to either (i) the metal-to-alkyne π backbonding or (ii) the M δ+ -C δ-bond polarity ( Lewis et al 1997). Pt.…”

Section: Resultsmentioning

confidence: 99%

Conjugated Platinum-Poly-Ynes with extended Arylene Ethynylenes

Naher

Mehdi

Ahmed

et al. 2015

J Bangladesh Acad Sci

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“…Each dimer is formed by two bridging COCH 2 CH 2 N ligands which are coordinated by one Pt(II) on one side via a Pt -N bond and to the second Pt(II) via Pt -C bond forming a six membered (-Pt -C -N -)2 ring . The Pt(II) ...Pt(II) separations are 3.407 (1) There are two Pt(II) dimers: pale yellow and yellow [82] and both contain two independent dimer molecules. In each case, the crystal structure consists of discrete dimeric molecules.…”

Section: Mecmentioning

confidence: 99%

“…The platinum in these derivatives are found in the oxidation states of zero [84,87], +1 [74], +2 [75,76,[79][80][81][82][83]89], and mixed valence Pt(I)(x2) plus Pt(II) [85] and Pt(II) plus Pt(IV) (x2) [86].…”

Section: Mecmentioning

confidence: 99%

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Stereochemistry of Platinum Organometallics

Melnı́k¹,

Garaj²,

Holloway³

2007

TOICJ

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Abstract:The organometallic chemistry of platinum covers a huge field, as shown by a recent survey covering the crystallographic and structural data of almost one thousand organometallic derivatives. About nine percent of those derivatives exist as isomers and are summarized in this review and include distortion (90 %), cis -trans (6%) and ligand isomerism (4%). These are discussed in terms of the coordination about the platinum atom, and correlations are drawn between donor atom, bond length and interbond angles, with attention to any trans -effect.Distortion isomers, differing only by degree of distortion in Pt-L bond lengths and L-Pt -L bond angles, are the most numerous. They are also spread over a wider range of oxidation states of platinum, (zero, +1, +2, +4, mixed valence +1 plus +2 and +2 plus +4), compared to cis-trans and ligand isomerism in which only +2 is found.

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Synthesis and characterisation of new acetylide-functionalised oligothiophenes and their dinuclear platinum complexes

Cited by 112 publications

References 23 publications

Highly Efficient Visible‐Light Driven Photochromism: Developments towards a Solid‐State Molecular Switch Operating through a Triplet‐Sensitised Pathway

Highly Efficient Visible‐Light Driven Photochromism: Developments towards a Solid‐State Molecular Switch Operating through a Triplet‐Sensitised Pathway

Conjugated Platinum-Poly-Ynes with extended Arylene Ethynylenes

Stereochemistry of Platinum Organometallics

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