Conjugated oligomers with terminal donor-acceptor substitution.

Conjugated oligomers represent a prominent class of compounds from a viewpoint of their theory, synthesis, and applications in materials science. Push-pull substitution with an electron donor D at one end of the conjugation and an electron acceptor A at the other end results in them having outstanding optical and electronical properties. This Review highlights fundamental synthetic strategies for the preparation of such oligomers with n repeat units (n=1, 2, 3, 4, ..) and the rules that govern their linear and nonlinear optical properties (absorption, frequency doubling and tripling). The unification of chemical, physical, and theoretical aspects with an interdisciplinary image of this class of compounds is attempted herein.

[1]  Sergei Tretiak,et al.  Density matrix analysis and simulation of electronic excitations in conjugated and aggregated molecules. , 2002, Chemical reviews.

[2]  H. Perkampus.  UV-VIS-Spektroskopie und ihre Anwendungen , 1986 .

[3]  S. Marder,et al.  The effect of varying ground-state aromaticity on the first molecular electronic hyperpolarizabilites of organic donor–acceptor molecules , 1993 .

[4]  J. Zyss,et al.  Very large quadratic nonlinearities in solution of two push-pull polyene series: Effect of the conjugation length and of the end groups , 1989 .

[5]  A. Tadjer,et al.  Studies of the energy spectrum of α, ω- substituted polymethine chains. II. Polymethine chains with odd number of methine groups , 1981 .

[6]  D. Hellwinkel,et al.  Phenylvinylog erweiterte Triphenylmethylium-Systeme , 1989 .

[7]  J. Roncali.  Oligothienylenevinylenes as a new class of multinanometer linear pi-conjugated systems for micro- and nanoelectronics. , 2000, Accounts of chemical research.

[8]  Andrew C. Grimsdale,et al.  Elektrolumineszierende konjugierte Polymere – Polymere erstrahlen in neuem Licht , 1998 .

[9]  M. Nohara,et al.  A New Series of Electroluminescent Organic Compounds , 1990 .

[10]  M. Neuenschwander,et al.  Synthese von ‘Push-Pull’-Diacetylenen†‡§ , 1983 .

[11]  Gerhard Wegner,et al.  Electronic Materials: The Oligomer Approach , 1998 .

[12]  K. Hirayama.  Absorption Spectra and Chemical Structures. I. Conjugated Polyenes and p-Polyphenyls , 1955 .

[13]  Seth R. Marder,et al.  Experimental investigations of organic molecular nonlinear optical polarizabilities. 1. Methods and results on benzene and stilbene derivatives , 1991 .

[14]  H. Meier,et al.  Methylium Ions with OPV Chains − New NIR Dyes , 2001 .

[15]  Seth R. Marder,et al.  Large Quadratic Hyperpolarizabilities with Donor–Acceptor Polyenes Exhibiting Optimum Bond Length Alternation: Correlation Between Structure and Hyperpolarizability , 1997 .

[16]  G I Stegeman,et al.  Large molecular third-order optical nonlinearities in polarized carotenoids. , 1997, Science.

[17]  J. Tour,et al.  Rapid Solution and Solid Phase Syntheses of Oligo(1,4-phenylene ethynylene)s with Thioester Termini: Molecular Scale Wires with Alligator Clips. Derivation of Iterative Reaction Efficiencies on a Polymer Support , 1997 .

[18]  C. Sauteret,et al.  The regularities observed in the second order hyperpolarizabilities of variously disubstituted benzenes , 1978 .

[19]  J. Perry,et al.  Valence-Bond Charge-Transfer Model for Nonlinear Optical Properties of Charge-Transfer Organic Molecules , 1994 .

[20]  Govind P. Agrawal,et al.  Delocalization and superalternation effects in the nonlinear susceptibilities of one-dimensional systems , 1976 .

[21]  M. Whiting,et al.  756. Researches on polyenes. Part VII. The preparation and electronic absorption spectra of homologous series of simple cyanines, merocyanines, and oxonols , 1960 .

[22]  Seth R. Marder,et al.  A Unified Description of Linear and Nonlinear Polarization in Organic Polymethine Dyes , 1994, Science.

[23]  Joseph Zyss,et al.  Chain length dependence of the third-order polarizability of disubstituted polyenes. Effects of end groups and conjugation length , 1993 .

[24]  Mark A. Ratner,et al.  Molecular and Macromolecular Nonlinear Optical Materials. Probing Architecture/Electronic Structure/Frequency Doubling Relationships via an SCF-LCAO MECI π Electron Formalism , 1988 .

[25]  J. Lehn,et al.  Large quadratic hyperpolarizabilities with donor-acceptor polyenes functionalized with strong donors. Comparison with donor-acceptor diphenylpolyenes , 1995 .

[26]  R. Gleiter,et al.  Hexasubstituted donor-acceptor benzenes as nonlinear optically active molecules with multiple charge-transfer transitions. , 2004, Chemistry.

[27]  Joseph Zyss,et al.  Nonlinear optical properties of organic molecules and crystals , 1987 .

[28]  M. Neuenschwander,et al.  Äthinyloge Säureamide und Urethane , 1968 .

[29]  C. Screttas,et al.  Organolithium reagents bearing nonlinear optical chromophores. Synthesis of triarylmethane dyes , 1999 .

[30]  R. Lapouyade,et al.  TIME-RESOLVED DUAL FLUORESCENCE OF PUSH-PULL STILBENES AT HIGH SOLUTE CONCENTRATION AND EXCITATION INTENSITY - EVIDENCE FOR AN EMITTING BICIMER , 1991 .

[31]  Seth R. Marder,et al.  Large First Hyperpolarizabilities in Push-Pull Polyenes by Tuning of the Bond Length Alternation and Aromaticity , 1994, Science.

[32]  John Stevens,et al.  Computational Modelling And Design Considerations Of Nonlinear Optical Materials , 1990, Optics & Photonics.

[33]  P. Günter,et al.  MOLECULAR ENGINEERING OF PUSH-PULL PHENYLPOLYENES FOR NONLINEAR OPTICS : IMPROVED SOLUBILITY, STABILITY, AND NONLINEARITIES , 1999 .

[34]  J. Oudar,et al.  Optical nonlinearities of conjugated molecules. Stilbene derivatives and highly polar aromatic compounds , 1977 .

[35]  J. Michl,et al.  Why is azulene blue and anthracene white? a simple mo picture , 1976 .

[36]  J. Segura,et al.  Functionalized oligoarylenes as building blocks for new organic materials , 2000 .

[37]  P. N. Butcher,et al.  The Elements of Nonlinear Optics , 1990 .

[38]  R. Wortmann,et al.  Organic Materials for Second-Order Non-Linear Optics , 1999 .

[39]  G. Manecke,et al.  Über Synthesen einiger oligomerer substituierter Arylenvinylene , 1970 .

[40]  V. P. Rao,et al.  Novel push-pull thiophenes for second order nonlinear optical applications , 1993 .

[41]  J. Oudar,et al.  Structural dependence of nonlinear-optical properties of methyl-(2,4-dinitrophenyl)-aminopropanoate crystals , 1982 .

[42]  U. Stalmach,et al.  Effective conjugation length and UV/vis spectra of oligomers , 1997 .

[43]  W. Berger,et al.  Untersuchungen zur Farbstofftheorie: Triarylmethanfarbstoffe der Biphenylreihe, II , 1951 .

[44]  R. Giesa.  Synthesis and Properties of Conjugated Poly(Aryleneethynylene)S , 1996 .

[45]  J. Oudar,et al.  Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment , 1977 .

[46]  A. Bianco,et al.  Molecules with enhanced negative third order vibrational polarizabilities: polymethine dyes and their vibrational spectra , 2001 .

[47]  H. Meier,et al.  Red‐ and Blue‐Shifts in Oligo(1,4‐phenyleneethynylene)s Having Terminal Donor−Acceptor Substitutions , 2004 .

[48]  Robert J. Twieg,et al.  DESIGN OF OPTIMIZED PHOTOREFRACTIVE POLYMERS : A NOVEL CLASS OF CHROMOPHORES , 1996 .

[49]  A. Facchetti,et al.  A distinctive example of the cooperative interplay of structure and environment in tuning of intramolecular charge transfer in second-order nonlinear optical chromophores. , 2003, Chemistry.

[50]  H. Meier,et al.  4,4′‐Distyrylazobenzol als Chromophor , 1992 .

[51]  J. Zyss,et al.  Nonlinear optical properties of asymmetric polyphenyls: Efficiency versus transparency trade-off , 1991 .

[52]  Rainer E. Martin,et al.  Lineare monodisperse π-konjugierte Oligomere: mehr als nur Modellverbindungen für Polymere , 1999 .

[53]  Herbert Meier,et al.  Die Photochemie stilbenoider Verbindungen und ihre materialwissenschaftlichen Aspekte , 1992 .

[54]  R. Lapouyade,et al.  Multiple luminescence from 'push-pull' diphenyl polyenes revealed by picosecond spectroscopy. Evidence for TICT and bicimer states , 1994 .

[55]  W. Baumann,et al.  Oligo(phenylenvinylene) mit terminaler Donor‐Acceptor‐Substitution , 2002 .

[56]  M. Blanchard‐Desce,et al.  A two-state description of (hyper) polarizabilities of push-pull molecules based on a two-form model , 1996 .

[57]  Herbert Meier,et al.  The Photochemistry of Stilbenoid Compounds and Their Role in Materials Technology , 1992 .

[58]  C. Kuhn.  Step potential model for non-linear optical properties of polyenes, push-pull polyenes and cyanines and the motion of solitons in long-chain cyanines , 1991 .

[59]  U. Bunz.  Poly(p-phenyleneethynylene)s by alkyne metathesis. , 2001, Accounts of chemical research.

[60]  S. Sengupta,et al.  Trivinylogs of Crystal Violet: synthesis and absorption properties of new near-IR dyes , 2000 .

[61]  W. Baumann,et al.  Oligo(phenylenevinylene)s with terminal donor-acceptor substitution. , 2002, Angewandte Chemie.

[62]  Peter Krämer,et al.  Second-order polarizability of donor-acceptor substituted oligothiophenes : substituent variation and conjugation length dependence , 1993 .

[63]  Urs Berger,et al.  Crystallization of Supramolecular Materials: Perhydrotriphenylene (PHTP) Inclusion Compounds with Nonlinear Optical Properties , 1996 .

[64]  K. Müllen,et al.  Extended π-systems in conjugated oligomers and polymers - the longer, the better? , 1993 .

[65]  N. Craig,et al.  Contribution to the Study of the Gauche Effect. The Complete Structure of the Anti Rotamer of 1,2-Difluoroethane , 1997 .

[66]  G. Jonusauskas,et al.  Photophysics of 4-dimethylamino 4′-cyanostilbene and model compounds: dual excited states revealed by sub-picosecond transient absorption and Kerr ellipsometry , 1997 .

[67]  R. Wortmann,et al.  Donor-acceptor oligoenes with a locked all-trans conformation: synthesis and linear and nonlinear optical properties. , 2002, Chemistry.

[68]  W. Rettig,et al.  Structure-photophysics correlations in a series of 4-(dialkylamino)stilbenes: intramolecular charge transfer in the excited state as related to the twist around the single bonds , 1993 .

[69]  J. Roncali.  Synthetic Principles for Bandgap Control in Linear pi-Conjugated Systems. , 1997, Chemical reviews.

[70]  Yaochun Shen,et al.  The Effect of Conjugation Length and Electron Donor Groups on the Second Order Nonlinear Polarizability of Cyano Substituted Aromatic Molecules , 1987 .

[71]  T. Pakula,et al.  Liquid crystals in the series of 2,4,6-tristyryl-1,3,5-triazines , 2004 .

[72]  N. Hush,et al.  Hole, electron and energy transfer through bridged systems. VIII: Soliton molecular switching in symmetry-broken brooker (polymethinecyanine) cations , 1993 .

[74]  S. Kovalenko,et al.  Femtosecond spectroscopy of p-dimethylaminocyanostilbene in solution—no evidence for dual fluorescence , 2002 .

[75]  J. Roncali,et al.  Vibrational and quantum-chemical study of push-pull chromophores for second-order nonlinear optics from rigidified thiophene-based pi-conjugating spacers. , 2003, Chemistry.

[76]  H. Meier,et al.  Star‐Shaped Compounds Having 1,3,5‐Triazine Cores , 2003 .

[77]  C. Tang,et al.  Length dependence of the second‐order optical nonlinearity in conjugated hydrocarbons , 1981 .

[78]  Josef Michl,et al.  Molecular Rods. 1. Simple Axial Rods. , 1999, Chemical reviews.

[79]  K. Hirayama.  Absorption Spectra and Chemical Structure. III. Effects of Substituents and Structure , 1955 .

[80]  B. K. Mishra,et al.  Cyanines during the 1990s: A Review. , 2000, Chemical reviews.

[81]  K. Müllen,et al.  Synthesis of α, ω-difunctionalized oligo- and poly(p-phenyleneethynylene)s , 1998 .

[82]  M. C. Flipse,et al.  Electronic and second-order nonlinear optical properties ofconformationally locked benzylideneanilines and biphenyls. The effect ofconformation on the first hyperpolarizability , 1997 .

[83]  T. Swager,et al.  The Molecular Wire Approach to Sensory Signal Amplification , 1998 .

[84]  H. Meier,et al.  Pentadecamer 2,5‐Dipropoxy‐1,4‐phenylenevinylene , 2002 .

[85]  H. Meier,et al.  Monodisperse Oligo(2,5-dipropoxy-1,4-phenyleneethynylene)s , 2002 .

[86]  Frank Kosteyn,et al.  4,4′‐Distyrylazobenzol als Mesogen , 1992 .

[87]  Seth R. Marder,et al.  Experimental investigations of organic molecular nonlinear optical polarizabilities. 2. A study of conjugation dependences , 1991 .

[88]  A. Hirsch,et al.  Dicyanopolyynes: A Homologuous Series of End‐Capped Linear sp Carbon , 1997 .

[89]  Jeffrey S. Moore.  Shape-Persistent Molecular Architectures of Nanoscale Dimension , 1997 .

[90]  Z. Bao,et al.  Synthetic chemistry for ultrapure, processable, and high-mobility organic transistor semiconductors. , 2001, Accounts of chemical research.

[91]  L. Bottomley,et al.  Bis(ferrocenyl)polymethine cations. A prototype molecular wire with redox-active end groups , 1995 .

[92]  H. Meier,et al.  Extension of conjugation leading to bathochromic or hypsochromic effects in OPV series. , 2004, Chemistry.

[93]  F. Effenberger,et al.  SYNTHESIS AND SOLVATOCHROMIC PROPERTIES OF DONOR-ACCEPTOR-SUBSTITUTED OLIGOTHIOPHENES , 1995 .

[94]  Laren M. Tolbert,et al.  Beyond the Cyanine Limit: Peierls Distortion and Symmetry Collapse in a Polymethine Dye , 1997 .

[95]  H. Meier,et al.  BATHOCHROMIC OR HYPSOCHROMIC EFFECTS VIA THE EXTENSION OF CONJUGATION : A STUDY OF STILBENOID SQUARAINES , 1999 .

[96]  H. Scheraga,et al.  Conformational Energy Calculations on Polypeptides and Proteins , 1994 .

[97]  G. Drefahl,et al.  Untersuchungen ber Stilbene, XIX. Polyphenyl-polyine , 1958 .

[98]  H. Meier,et al.  The effect of 2,2-dicyanovinyl groups as electron acceptors in push–pull substituted oligo(1,4-phenylenevinylene)s , 2003 .

[99]  Seth R. Marder,et al.  Electric Field Modulated Nonlinear Optical Properties of Donor-Acceptor Polyenes: Sum-Over-States Investigation of the Relationship between Molecular Polarizabilities (.alpha., .beta., and .gamma.) and Bond Length Alternation , 1994 .

[100]  J. Zyss,et al.  Chain-length dependence of the quadratic hyperpolarizability of push-pull polyenes and carotenoids. Effect of end groups and conjugation path , 1994 .

[101]  J. Gladysz,et al.  Carbon in one dimension: structural analysis of the higher conjugated polyynes. , 2003, Chemical reviews.

[102]  H. Meier,et al.  NIR Absorbing Squaraines by Extension of the Conjugation with (Aminothiazolyl)ethenyl Groups , 2004 .

[103]  K. Hafner,et al.  Ethynylogous Amides and Urethanes , 1968 .

[104]  J. Perry,et al.  Relation Between Bond-Length Alternation and Second Electronic Hyperpolarizability of Conjugated Organic Molecules , 1993, Science.

[105]  A. Jen,et al.  Nonlinear optical chromophores with configuration-locked polyenes possessing enhanced thermal stability and chemical stability , 1998 .

[106]  Herbert Meier,et al.  Preparation and Nonlinear Optics of Monodisperse Oligo(1,4‐phenyleneethynylene)s , 2001 .

[107]  Richard R. Schrock,et al.  Third-order microscopic nonlinearities of very long chain polyenes: saturation phenomena and conformational effects , 1999 .

[108]  H. Meier,et al.  3,6‐Bis(2‐arylethenyl)‐1,2,4,5‐tetrazine – Synthese, Flüssigkristallinität und Photochemie , 1995 .

[109]  U. Scherf.  Oligo- and Polyarylenes, Oligo- and Polyarylenevinylenes , 1999 .

[110]  Manfred Schmidt,et al.  Structure of poly(diacetylenes) in solution , 1984 .

[111]  P. Brocklehurst,et al.  The effect of terminal nitro and amino groups on the electronic spectra of conjugated hydrocarbon systems , 1960 .

[112]  Hans-Joachim Freund,et al.  An MNDO and CNDO / S(S + DES CI) study on the structural and electronic properties of a model squaraine dye and related cyanine , 1986 .

[113]  J. Nicoud,et al.  Synthesis and computational studies of hyperpolarizable zig-zag chromophores , 1994 .

[114]  U. Bunz,et al.  Poly(aryleneethynylene)s: Syntheses, Properties, Structures, and Applications. , 2000, Chemical reviews.

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

[116]  F. Würthner,et al.  5‐Dimethylamino‐5′‐nitro‐2, 2′‐bithiophene—a New Dye with Pronounced Positive Solvatochromism , 1993 .

[117]  B. Cho,et al.  Synthesis and nonlinear optical properties of 1,3,5-methoxy-2,4,6-tris(styryl)benzene derivatives. , 2002, Organic letters.

[118]  J. Zyss,et al.  Push–pull polyenes and carotenoids: synthesis and non-linear optical properties , 1988 .

[119]  J. Fauvarque,et al.  Efficient palladium-catalyzed synthesis of unsymmetrical donor—acceptor biaryls and polyaryls , 1990 .

[120]  F. Gallego-Gómez,et al.  ATOP dyes. optimization of a multifunctional merocyanine chromophore for high refractive index modulation in photorefractive materials. , 2001, Journal of the American Chemical Society.

[121]  V. J. Docherty,et al.  Non-linear optical properties of organic molecules. Part 2. Effect of conjugation length and molecular volume on the calculated hyperpolarisabilities of polyphenyls and polyenes , 1987 .

[122]  G. Lewis,et al.  The Color of Organic Substances. , 1939 .

[123]  Katarzyna Lukaszuk,et al.  Electrooptical Chromophores for Nonlinear Optical and Photorefractive Applications , 1999 .

[124]  David J. Williams,et al.  Introduction to Nonlinear Optical Effects in Molecules and Polymers , 1991 .

[125]  Mireille Blanchard-Desce,et al.  Intramolecular charge transfer in donor-acceptor molecules , 1990 .

[126]  Frank Würthner,et al.  5‐Dimethylamino‐5′‐nitro‐2,2′‐bithiophen ‐ ein neuer Farbstoff mit ausgeprägter positiver Solvatochromie , 1993 .

[127]  J. Tour.  Conjugated Macromolecules of Precise Length and Constitution. Organic Synthesis for the Construction of Nanoarchitectures. , 1996, Chemical reviews.

[128]  M. Lehmann,et al.  Star-shaped conjugated compounds forming nematic discotic systems , 2004 .

[129]  R. Hierle,et al.  Design and Synthesis of Push−Pull Chromophores for Second-Order Nonlinear Optics Derived from Rigidified Thiophene-Based π-Conjugating Spacers , 2002 .

[130]  D. Burland,et al.  Optical Nonlinearities In Chemistry: Introduction , 1994 .

[131]  S. Mukamel,et al.  ORIGIN, SCALING, AND SATURATION OF SECOND ORDER POLARIZABILITIES IN DONOR/ACCEPTOR POLYENES , 1998 .

[132]  M. C. Flipse,et al.  The determination of first hyperpolarizabilities β using hyper-Rayleigh scattering : a caveat , 1995 .

[133]  Wolfgang Rettig,et al.  Structural changes accompanying intramolecular electron transfer: focus on twisted intramolecular charge-transfer states and structures. , 2003, Chemical reviews.

[134]  J. Gähde,et al.  Conjugated Polymers and Related Materials , 1994 .

[135]  R. Lapouyade,et al.  Dual fluorescence in trans-4-dimethylamino-4'-cyanostilbene revealed by picosecond time-resolved spectroscopy: A possible new , 1988 .

[136]  J. Tour,et al.  Molecular electronics. Synthesis and testing of components. , 2000, Accounts of chemical research.

[137]  R. Radeglia,et al.  Revision der Lewis-Calvin-Regel zur charakterisierung vinyloger. Polyen- und polymethinähnlicher verbindungen☆ , 1971 .

[138]  C. Flytzanis,et al.  Nonlinear optical properties of one-dimensional semiconductors and conjugated polymers , 1978 .

[139]  Seth R. Marder,et al.  Effect of Molecular Polarization on Bond-Length Alternation, Linear Polarizability, First and Second Hyperpolarizability in Donor-Acceptor Polyenes as a Function of Chain Length , 1995 .

[140]  Rainer E. Martin,et al.  Linear Monodisperse π-Conjugated Oligomers: Model Compounds for Polymers and More. , 1999, Angewandte Chemie.