Structural characterisation of a series of acetylide-functionalised oligopyridines and the synthesis, characterisation and optical spectroscopy of platinum di-ynes and poly-ynes containing oligopyridyl linker groups in the backbone

Khan, Muhammad S.; Al-Mandhary, Muna R. A.; Al‐Suti, Mohammed K.; Hisahm, Abdul Khader; Raithby, Paul R.; Ahrens, Birte; Mahon, Mary F.; Male, Louise; Marseglia, E.; Tedesco, Emilio; Friend, Richard H.; Köhler, Anna; Feeder, Neil; Teat, Simon J.

doi:10.1039/b110658a

Cited by 87 publications

(70 citation statements)

References 47 publications

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“…[78][79][80] Macromol hindering the conjugation between the pyridine rings and perhaps increasing the number of pyridine units, which would enhance the electron-accepting ability of the polymers. [79] Both polymers 74 and 75 are non-conductors in the undoped state but become semiconducting upon doping with iodine vapour (conductivity ¼ 2.5 Â 10 À3 and 3.4 Â 10 À3 S Á cm À1 for 74 and 75, respectively). This is consistent with the enhanced p-electron delocalization in 75 upon quaternization of the pyridine.…”

Section: Scheme 24mentioning

confidence: 99%

Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans‐Bis(para‐ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives

Wong

Harvey

2010

Macromol. Rapid Commun.

186

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This review article surveys the electronic and photophysical properties of conjugated organometallic polymers built upon the title compound and its related derivatives focussing primarily on systems investigated in our laboratories. The general structure of the polymers is (trans-bis(para-ethynylbenzene)bis(phosphine)platinum(II)-G)(n) where G is a conjugated group such as thiophene, fluorene, carbazole, substituted silole, quinone derivative, and metalloporphyrin residue, or a non-conjugated main-group moiety. Systems based on substituted phenylene units and other related fused rings are also discussed. The phosphine ligands are generally triethyl- or tri-n-butylphosphine groups. These trans-platinum(II) polymers and the corresponding model compounds are compared to the corresponding ortho-derivatives in the quinone series, and the newly prepared paracyclophane-containing polymers. For the porphyrin series, a comparison of fully conjugated oligomers exhibiting the general structure (trans-bis(para-ethynyl(zinc(porphyrin)))bis(phosphine)platinum(II))(n) (i.e., the C(6) H(4) group is absent from the main chain) will be made. This contribution also includes a description of the properties of the mononuclear chromophore itself, properties that define those of the polymers. Potential applications with regard to electronic and optical devices will be highlighted. These soluble and stable materials feature both the processing advantages of polymers and the functionality provided by the presence of metal centers. These multifunctional organometallic polyyne polymers exhibit convenient structural variability as well as optical and electronic properties, which renders them important for use in different research domains as chemical sensors and sensor protectors, as converters for light/electricity signals, and as patternable precursors to magnetic metal alloy nanoparticles.

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Section: Scheme 24mentioning

confidence: 99%

Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans‐Bis(para‐ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives

Wong

Harvey

2010

Macromol. Rapid Commun.

186

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“…Table 2 compares the E g values and other photophysical data of our new materials with some known platinum(II) polyynes in the literature in terms of their p-conjugative ability in which the bithiazole ring tends to reduce E g and red-shift the l max value relative to their bithienyl and bipyridyl counterparts. [29,31,32] By virtue of the electron-accepting bithiazole ring and its Table 2). We consider that the D-A interaction already present in the spacer is remarkably enhanced by the electronic system in the polymer backbone that contains the electron-rich platinum ion in the Pt compounds, which gives rise to a lowering of the optical gap.…”

Section: Photophysical Thermal and Redox Propertiesmentioning

confidence: 99%

Organometallic Polymer Light‐Emitting Diodes Derived from a Platinum(II) Polyyne Containing the Bithiazole Ring

Wong

Zhou

et al. 2008

Macro Chemistry & Physics

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The synthesis, thermal, and photoluminescence properties of novel platinum metallopolyynes of bithiazole derivatives trans‐[Pt(PR3)2‐C≡C‐Ar‐C≡C]n (Ar = 4,4′‐dibutyl‐2,2′‐bithiazole‐5,5′‐diyl P1; 4,4′‐dinonyl‐2,2′‐bithiazole‐5,5′‐diyl P2) and their molecular model complexes are described. The structural properties of the dinuclear model compound for P1 have been examined by X‐ray crystallography. In view of the electron‐donating and electron‐withdrawing nature of the thiazole rings in the main chain, a strong π‐conjugated system that features unique donor–acceptor interactions is created, which results in optical bandgaps of 2.40 eV. The optical gap of the polymer is notably reduced as compared to that for the more electron‐rich bithienyl analogue. Multi‐layer polymer light‐emitting diodes have been fabricated with the metallopolymer as the emitting layer, which give a green light color with the Commission Internationale de L'Eclairage (CIE) chromaticity coordinates of (0.26, 0.58) at 8 V.magnified image

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“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] In the chemistry of alkynyl platinum complexes increasing attention has been paid to the study of the spectroscopic and luminescence behavior of discrete polynuclear platinum complexes containing alkynyl bridging ligands because of their ability to modulate them by metal-metal (Pt···Pt, Pt···M) and h 2 -metal alkynyl bonding interactions. [5,[22][23][24][25][26][27][28][29][30][31] Furthermore, polynuclear transition-metal complexes with neutral pyrazoles (HRpz) or anionic pyrazolates (Rpz) as ligands have attracted much attention due to their versatile structures and properties.…”

Section: Introductionmentioning

confidence: 99%

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

Forniés

Fuertes

Martín

et al. 2006

Chemistry A European J

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This work describes the synthesis of cis-[Pt(C[triple bond]CPh)2(Hdmpz)2] (1) and its use as a precursor for the preparation of homo- and heteropolynuclear complexes. Double deprotonation of compound 1 with readily available M(I) (M = Cu, Ag, Au) or M(II) (M = Pd, Pt) species affords the discrete hexanuclear clusters [{PtM2(mu-C[triple bond]CPh)2(mu-dmpz)(2)}(2)] [M = Cu (2), Ag (3), Au (4)], in which both "Pt(C[triple bond]CPh)2(dmpz)(2)" fragments are connected by four d(10) metal centers, and are stabilized by alkynyl and dimethylpyrazolate bridging ligands, or the trinuclear complexes [Pt(mu-C[triple bond]CPh)2(mu-dmpz)(2){M(C/\P)}2] (M = Pd (5), Pt (6); C/\P = CH(2)-C(6)H(4)-P(o-tolyl)2-kappaC,P), respectively. The X-ray structures of complexes 1-4 and 6 are reported. The X-ray structure of the platinum-copper derivative 2 shows that all copper centers exhibit similar local geometry being linearly coordinated to a nitrogen atom and eta(2) to one alkynyl fragment. However in the related platinum-silver (3) and platinum-gold (4) derivatives the silver and gold atoms present three different coordination environments. The complexes have been studied by absorption and emission spectroscopy. The hexanuclear complexes exhibit bright luminescence in the solid state and in fluid solution (except 4 in the solid state at 298 K). Dual long-lived emission is observed, being clearly resolved in low-temperature rigid media. The low-energy emission is ascribed to MLM'CT Pt(d)/pi(C[triple bond]CPh)-->Pt(p(z))/M'(sp)/pi*(C[triple bond]CPh) modified by metal-metal interactions whereas the high-energy emission is tentatively attributed to an emissive state derived from dimethylpyrazolate-to-metal (d(10)) LM'CT transitions pi(dmpz)-->M'(d(10)).

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Structural characterisation of a series of acetylide-functionalised oligopyridines and the synthesis, characterisation and optical spectroscopy of platinum di-ynes and poly-ynes containing oligopyridyl linker groups in the backbone

Cited by 87 publications

References 47 publications

Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans‐Bis(para‐ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives

Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans‐Bis(para‐ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives

Organometallic Polymer Light‐Emitting Diodes Derived from a Platinum(II) Polyyne Containing the Bithiazole Ring

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

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