Spectral and Photophysical Studies of Poly[2,6-(1,5-dioctylnaphthalene)]thiophenes

A complete spectroscopic and photophysical study of three alternating naphthalene-α-thiophene copolymers was undertaken in solution (room and low temperature) and in the solid state (thin films in a Zeonex matrix). The study comprises absorption, emission, and triplet−triplet spectra together with quantitative measurements of quantum yield (fluorescence, intersystem-crossing, internal conversion, and singlet oxygen formation) lifetimes and singlet and triplet energies. The overall data allow the determination of the rate constants for all the decay processes. Comparison between the behavior of analogous 1-naphthyl(oligo)thiophenes and the 2,6-naphthalene(oligo)thiophene copolymers allows several important observations. First, the polymers display higher fluorescence quantum yields and lower S1∼∼→T1 intersystem-crossing yields than the oligomers. This can be attributed to the presence of the 1,5-dioctyloxynaphthalene groups in the copolymers leading to a more rigid polymer backbone, which decreases radiati...

[1]  H. Pan,et al.  Poly(2,5‐bis(2‐thienyl)‐3,6‐dialkylthieno [3,2‐b]thiophene)s—High‐Mobility Semiconductors for Thin‐Film Transistors , 2006 .

[2]  Rita Cagnoli,et al.  One-Pot Synthesis of Symmetric Octithiophenes from Asymmetric β-Alkylsulfanyl Bithiophenes , 2006 .

[3]  U. Scherf,et al.  Spectral and photophysical studies on cruciform oligothiophenes in solution and the solid state. , 2006, The journal of physical chemistry. B.

[4]  L. Alcácer,et al.  Triplet-state and singlet oxygen formation in fluorene-based alternating copolymers. , 2006, The journal of physical chemistry. B.

[5]  Yongfang Li,et al.  Synthesis and properties of polythiophenes with conjugated side‐chains containing carbon–carbon double and triple bonds , 2006 .

[6]  R. Becker,et al.  Photophysical Studies of α,ω-Dicyano-oligothiophenes NC(C4H2S)nCN (n = 1−6) , 2006 .

[7]  Philippe Blanchard,et al.  Fine tuning of the electronic properties of linear pi-conjugated oligomers by covalent bridging. , 2006, Chemistry.

[8]  N. Somanathan,et al.  OPTICAL PROPERTIES OF FUNCTIONALIZED POLYTHIOPHENES , 2005 .

[9]  F. Wudl,et al.  Light‐Emitting Polythiophenes , 2005, Advanced Materials.

[10]  U. Scherf,et al.  Synthesis and spectroscopy of an oligophenyl based cruciform with remarkable π–π assisted folding , 2005 .

[11]  P. Frère,et al.  Oligothienylenevinylenes incorporating 3,4-ethylenedioxythiophene (EDOT) units , 2005 .

[12]  R. Cingolani,et al.  Nonradiative relaxation in thiophene-S,S-dioxide derivatives: the role of the environment. , 2005, The journal of physical chemistry. B.

[13]  W. Fann,et al.  Direct Measurement of the Triplet Quantum Yield of Poly(3-dodecylthiophene) in Solution , 2004 .

[14]  U. Scherf,et al.  Semiconducting Polymers via Microwave‐Assisted Suzuki and Stille Cross‐Coupling Reactions , 2004 .

[15]  Zhi-Kuan Chen,et al.  Poly(naphthylenethiophene)s and poly(naphthylenevinylenephenylenevinylene)s: effect of naphthalene positional isomers on the light emitting properties of their polymers , 2004 .

[16]  U. Scherf,et al.  Hole formation and transfer in poly[9,9-di(ethylhexyl)fluorene] and an amine end-capped derivative in solution , 2004 .

[17]  E. Oliveros,et al.  Effect of the Media on the Quantum Yield of Singlet Oxygen (O2(1Δg)) Production by 9H-Fluoren-9-one: Solvents and Solvent Mixtures , 2003 .

[18]  M. Andersson,et al.  Photophysics of thiophene based polymers in solution: The role of nonradiative decay processes , 2003 .

[19]  E. Bittner,et al.  Spin-dependent electron-hole capture kinetics in luminescent conjugated polymers. , 2002, Physical review letters.

[20]  Hugh D. Burrows,et al.  S1∼>T1 intersystem crossing in π-conjugated organic polymers , 2001 .

[21]  J. S. D. Melo,et al.  Photophysical and theoretical studies of naphthalene-substituted oligothiophenes , 2001 .

[22]  L. J. Hartwell,et al.  Triplet energies of pi-conjugated polymers. , 2001, Physical review letters.

[23]  G. Striker,et al.  Photochromicity and fluorescence lifetimes of green fluorescent protein , 1999 .

[24]  Donal D. C. Bradley,et al.  MONODOMAIN ALIGNMENT OF THERMOTROPIC FLUORENE COPOLYMERS , 1999 .

[25]  A. Monkman,et al.  Measurement of the S0–T1 energy gap in poly(2-methoxy,5-(2′-ethyl-hexoxy)–p-phenylenevinylene) by triplet–triplet energy transfer , 1999 .

[26]  J. Sérgio Seixas de Melo,et al.  Comprehensive Evaluation of the Absorption, Photophysical, Energy Transfer, Structural, and Theoretical Properties of α-Oligothiophenes with One to Seven Rings , 1996 .

[27]  R. Brown.  Excited states and free radicals in biology and medicine: edited by R.V. Bensasson, E.J. Land and T.G. Truscott, Oxford University Press, 1993 , 1995 .

[28]  S. Rhee,et al.  Photoluminescence properties of various polythiophene derivatives , 1994 .

[29]  F. Cacialli,et al.  Electrochemical and luminescent properties of poly(fluorene) derivatives for optoelectronic applications , 2001 .

[30]  C. Kumar,et al.  Aromatic thioketone triplets and their quenching behaviour towards oxygen and di-t-butylnitroxy radical. A laser-flash-photolysis study , 1984 .

[31]  Steven L. Murov,et al.  Handbook of photochemistry , 1973 .