Synthesis and optical spectroscopy of linear long-chain di-terminal alkynes and their Pt-σ-acetylide polymeric complexes

A variety of straight-chain alkynes with extended π-conjugation through benzene, anthracene and thiophene linker units in the backbone, H—CC—R′—CC—R—CC—R′—CC—H (R =p-C6H4, 9,10-C14H8, 2,5-C4H2S; R′=p-C6H4, p-C6H4-C6H4-p) has been synthesized. The alkynyl chromophores with an anthracene spacer unit are highly emissive in solution with luminescence quantum yields of up to 0.5. The platinum σ-acetylide polymeric complexes of the above ligands show strong absorptions associated with metal-to-alkynyl ligand charge transfer (MLCT) transitions. It is clear that the π-conjugation is maintained through the metal centres and the optical gap for the polymer, [graphic omitted]Pt(PBun3)2-CC-p-C6H4-CC-9,10-C14H8-CC-p-C6H4-CC[graphic omitted]n is lower than for the complexes [graphic omitted]Pt(PBn3)2-CC-R′-CC-R-CC-R′-CC[graphic omitted]n(R =p-C6H4, 2,5-C4H2S; R′=p-C6H4; p-C6H4-C6H4-p).

[1]  D. Lichtenberger,et al.  Investigation of metal-d.pi.-butadiynyl-.pi. interactions in (.eta.5-C5H5)(CO)2FeC.tplbond.CC.tplbond.CH using photoelectron spectroscopy , 1993 .

[2]  B. Trost,et al.  Metal-mediated approach to enynes , 1987 .

[3]  S. Guha,et al.  Measurement of the third-order hyperpolarizability of platinum poly-ynes. , 1989, Optics letters.

[4]  N. Kostić,et al.  Molecular orbital study of bonding, conformations, and reactivity of transition-metal complexes containing unsaturated organic ligands. Electrophilic and nucleophilic additions to acetylide, vinylidene, vinyl, and carbene ligands , 1982 .

[5]  A. P. Davey,et al.  Non-linear optical properties of Group 10 metal alkynyls and their polymers , 1991 .

[6]  J. Miller,et al.  Standards in Flourescence Spectrometry , 1981 .

[7]  E. M. Graham,et al.  The electronic structure and second-order nonlinear optical properties of donor-acceptor acetylenes: a detailed investigation of structure-property relationships , 1991 .

[8]  L. Cassar.  Synthesis of aryl- and vinyl-substituted acetylene derivatives by the use of nickel and palladium complexes , 1975 .

[9]  R. Friend,et al.  Materials chemistry communications. Synthesis and optical spectroscopy of monomeric and polymeric cobalt σ-acetylide complexes , 1992 .

[10]  R. Friend,et al.  Di-, tri-, pseudo-di- and pseudo-tetra-acetylenic polymers of platinum: Synthesis, characterization and optical spectra , 1992 .

[11]  E. Chauchard,et al.  Four-Wave Mixing in Metal Poly-Ynes , 1987 .

[12]  T. Lanza,et al.  6-substituted indoles from o-halonitrobenzenes , 1986 .

[13]  K. Sonogashira,et al.  Linear polymers containing transition metals in the main chain , 1981 .

[14]  R. Nast,et al.  Metallorganische verbindungen des 1,4-diethinylbenzols vom typ p-C6Hn4(C=CMR3)2 (M = Si, Ge, Sn, Pb) , 1979 .

[15]  N. Leonard,et al.  Rearrangements of azabiphenylenes: the impact of nitrogen number and position , 1985 .

[16]  H. A. Dieck,et al.  Palladium catalyzed synthesis of aryl, heterocyclic and vinylic acetylene derivatives , 1975 .

[17]  K. Sonogashira,et al.  Studies of Poly-yne Polymers Containing Transition Metals in the Main Chain. 2. Synthesis of Poly[trans-bis(tri-n-butylphosphine)platinum 1,4-butadiynediyl] and Evidence of a Rodlike Structure , 1978 .

[18]  W. Blau,et al.  Nonlinear Optical Studies of Transition Metal Containing Conjugated Organic Monomeric and Polymeric Systems , 1991 .

[19]  V. P. Rao,et al.  Functionalized thiophenes: second-order nonlinear optical materials , 1993 .

[20]  R. L. Dekock,et al.  Ultraviolet photoelectron spectra of square-planar complexes of nickel triad metals. 3. He(I) and He(II) spectra of trans-[(PEt3)2MXY] (M = Pd, Pt; X = Y = C.tplbond.CH, C.tplbond.CMe, C.tplbond.N; X = Cl, Y = C.tplbond.N) and Hartree-Fock-Slater calculations on model compounds , 1984 .

[21]  A. Kakkar,et al.  SYNTHESIS OF NOVEL RIGID ROD IRON METAL CONTAINING POLYYNE POLYMERS , 1991 .

[22]  R. Katoh,et al.  Observation of fluorescence from higher excited states in an anthracene crystal , 1993 .

[23]  M. J. Adams,et al.  Determination of the absolute quantum efficiency of luminescence of solid materials employing photoacoustic spectroscopy , 1980 .

[24]  R. Friend,et al.  Optical excitations in transition metal containing poly-ynes , 1993 .

[25]  Brian F. G. Johnson,et al.  Synthesis of monomeric and oligomeric bis(acetylide) complexes of platinum and rhodium , 1991 .

[26]  D. Lichtenberger,et al.  Metal-Acetylide Bonding in (η5-C5H5)Fe(CO)2C≡CR Compounds. Measures of Metal-dπ-Acetylide-π Interactions from Photoelectron Spectroscopy , 1993 .

[27]  A. Haim,et al.  Synthesis of 1,4‐bis(4‐pyridyl)butadiyne , 1984 .

[28]  Y. Tohda,et al.  A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines , 1975 .

[29]  K. Sonogashira,et al.  Studies on polyyne polymers containing transition metals in the main chain. VII. Synthesis and characterization of palladium‐polyyne polymers , 1982 .

[30]  Seth R. Marder,et al.  Materials for Nonlinear Optics Chemical Perspectives , 1991 .

[31]  R. Friend,et al.  Synthesis and optical spectroscopy of platinum-metal-containing di- and tri-acetylenic polymers , 1991 .

[32]  G. Whitesides,et al.  Synthesis of high carbon materials from acetylenic precursors. Preparation of aromatic monomers bearing multiple ethynyl groups , 1988 .

[33]  S. Guha,et al.  Third-order optical non-linearity in metal-containing organic polymers , 1987 .

[34]  N. Taylor,et al.  Synthesis of mononuclear, dinuctear and oligomeric rigid-rod acetylide complexes of rhodium, and the molecular structure of [Rh(PMe3)4(CC–p-C6H4–CC)Rh(PMe3)4] , 1991 .

[35]  A. R. Williams,et al.  Relative fluorescence quantum yields using a computer-controlled luminescence spectrometer , 1983 .

[36]  M. Kertész,et al.  Metal oligo-yne polymers: electronic structures of [-(L)nMC.tplbond.CRC.tplbond.C-]x polymers , 1993 .

[37]  P. Hanhela,et al.  Synthesis and evaluation of fluorescent materials for colour control of peroxyoxalate chemiluminescence. III. Yellow and red fluorescent emitters , 1981 .

[38]  Brian F. G. Johnson,et al.  Synthesis of monomeric, oligomeric and polymeric σ-acetylide complexes of platinum, palladium, nickel and rhodium , 1992 .