Exploring potentialities and limitations of stapled o-oligo(phenyleneethynylene)s (o-OPEs) as efficient circularly polarized luminescence emitters.

In this paper, we have studied the chiroptical properties of a family of o-oligo(phenyleneethynylene) (o-OPE) derivatives with different steric hindrance. Experimental results show high dissymmetry factors (gabs and glum up to 1.1 × 10-2 ) and very similar electronic circular dichroism (ECD) and circularly polarized luminescence (CPL) for all the derivatives that make this basic o-OPE scaffold a robust pure organic emitter. Vibrational circular dichroism spectra are used to characterize conformational properties in solution. Density functional theory and time-dependent density functional theory calculations support experimental results also proving that ECD and CPL are almost exclusively linked to helical moiety and not to size or conformation of substituents. As chiroptical properties of these emitters are independent of substituents, this OPE scaffold can be used as basic skeleton for the design of sensing probes with high CPL efficiencies.

[1]  Francesco Zinna,et al.  Enantiopure Cycloiridiated Complexes Bearing a Pentahelicenic N-Heterocyclic Carbene and Displaying Long-Lived Circularly Polarized Phosphorescence. , 2017, Angewandte Chemie.

[2]  D. Stalke,et al.  Chiral-at-Metal Phosphorescent Square-Planar Pt(II)-Complexes from an Achiral Organometallic Ligand. , 2017, Journal of the American Chemical Society.

[3]  I. García‐Moreno,et al.  Chiral Organic Dyes Endowed with Circularly Polarized Laser Emission. , 2017, The journal of physical chemistry. C, Nanomaterials and interfaces.

[4]  J. Autschbach,et al.  Synthesis and Chiroptical Properties of Hexa-, Octa-, and Deca-azaborahelicenes: Influence of Helicene Size and of the Number of Boron Atoms. , 2017, Chemistry.

[5]  Tadashi Mori,et al.  Propeller Chirality of Boron Heptaaryldipyrromethene: Unprecedented Supramolecular Dimerization and Chiroptical Properties. , 2017, The journal of physical chemistry letters.

[6]  K. Monde,et al.  Analysis of Configuration and Conformation of Furanose Ring in Carbohydrate and Nucleoside by Vibrational Circular Dichroism. , 2017, Organic letters.

[7]  R. Pal,et al.  Very bright, enantiopure europium(iii) complexes allow time-gated chiral contrast imaging. , 2016, Chemical communications.

[8]  Giuseppe Mazzeo,et al.  Circularly Polarized Luminescence: A Review of Experimental and Theoretical Aspects. , 2016, Chirality.

[9]  K. Monde,et al.  Studying the stereostructures of biomolecules and their analogs by vibrational circular dichroism , 2016 .

[10]  Yan‐Song Zheng,et al.  The Fixed Propeller-Like Conformation of Tetraphenylethylene that Reveals Aggregation-Induced Emission Effect, Chiral Recognition, and Enhanced Chiroptical Property. , 2016, Journal of the American Chemical Society.

[11]  Xu-Hua Wang,et al.  Circularly Polarized Phosphorescent Electroluminescence with a High Dissymmetry Factor from PHOLEDs Based on a Platinahelicene. , 2016, Journal of the American Chemical Society.

[12]  P. Polavarapu Structural Analysis Using Chiroptical Spectroscopy: Insights and Cautions. , 2016, Chirality.

[13]  S. Hirata,et al.  Circularly Polarized Persistent Room-Temperature Phosphorescence from Metal-Free Chiral Aromatics in Air. , 2016, The journal of physical chemistry letters.

[14]  E. Vauthey,et al.  Functionalized cationic [4]helicenes with unique tuning of absorption, fluorescence and chiroptical properties up to the far-red range , 2016, Chemical science.

[15]  Bernard Geffroy,et al.  Design and Synthesis of New Circularly Polarized Thermally Activated Delayed Fluorescence Emitters. , 2016, Journal of the American Chemical Society.

[16]  T. Kawai,et al.  Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand. , 2016, Angewandte Chemie.

[17]  M. Ortiz,et al.  Circularly Polarized Luminescence from Simple Organic Molecules , 2015 .

[18]  Tsuyoshi Kawai,et al.  Circularly Polarized Luminescence in Chiral Molecules and Supramolecular Assemblies. , 2015, The journal of physical chemistry letters.

[19]  M. Weimar,et al.  Chiroptical studies on brevianamide B: vibrational and electronic circular dichroism confronted. , 2015, The Journal of organic chemistry.

[20]  Francesco Zinna,et al.  Highly Circularly Polarized Electroluminescence from a Chiral Europium Complex , 2015, Advanced materials.

[21]  K. Hayashi,et al.  A doubly alkynylpyrene-threaded [4]rotaxane that exhibits strong circularly polarized luminescence from the spatially restricted excimer. , 2014, Angewandte Chemie.

[22]  K. Akagi,et al.  Dynamic switching of the circularly polarized luminescence of disubstituted polyacetylene by selective transmission through a thermotropic chiral nematic liquid crystal. , 2014, Angewandte Chemie.

[23]  S. Lepri,et al.  Importance of C*-H based modes and large amplitude motion effects in vibrational circular dichroism spectra: the case of the chiral adduct of dimethyl fumarate and anthracene. , 2014, The journal of physical chemistry. A.

[24]  G. Longhi,et al.  Chiroptical spectroscopic techniques based on fluorescence , 2014, Methods and applications in fluorescence.

[25]  Ken Tanaka,et al.  Enantioselective synthesis and enhanced circularly polarized luminescence of S-shaped double azahelicenes. , 2014, Journal of the American Chemical Society.

[26]  Kirandeep K. Deol,et al.  Straightforward access to mono- and bis-cycloplatinated helicenes displaying circularly polarized phosphorescence by using crystallization resolution methods , 2014 .

[27]  N. Tokitoh,et al.  Planar chiral tetrasubstituted [2.2]paracyclophane: optical resolution and functionalization. , 2014, Journal of the American Chemical Society.

[28]  Gilles Muller,et al.  Circularly Polarized Luminescence by Visible-Light Absorption in a Chiral O-BODIPY Dye: Unprecedented Design of CPL Organic Molecules from Achiral Chromophores , 2014, Journal of the American Chemical Society.

[29]  J. García‐Ruiz,et al.  Versatile bottom-up approach to stapled π-conjugated helical scaffolds: synthesis and chiroptical properties of cyclic o-phenylene ethynylene oligomers. , 2012, Angewandte Chemie.

[30]  Xuhui Huang,et al.  What makes efficient circularly polarised luminescence in the condensed phase: aggregation-induced circular dichroism and light emission , 2012 .

[31]  P. Stephens,et al.  VCD Spectroscopy for Organic Chemists , 2012 .

[32]  K. Noguchi,et al.  Rhodium-catalyzed enantioselective synthesis, crystal structures, and photophysical properties of helically chiral 1,1'-bitriphenylenes. , 2012, Journal of the American Chemical Society.

[33]  G. Muller,et al.  Circularly Polarized Luminescence Spectroscopy and Emission‐Detected Circular Dichroism , 2012 .

[34]  Laurence A. Nafie,et al.  Vibrational Optical Activity: Principles and Applications , 2011 .

[35]  Guochun Yang,et al.  Vibrational circular dichroism spectroscopy of chiral molecules. , 2011, Topics in current chemistry.

[36]  G. Longhi,et al.  Revisiting with Updated Hardware an Old Spectroscopic Technique: Circularly Polarized Luminescence , 2010, Applied spectroscopy.

[37]  G. Longhi,et al.  Assessment of configurational and conformational properties of naringenin by vibrational circular dichroism. , 2009, Chirality.

[38]  Yunjie Xu,et al.  Chirality transfer through hydrogen-bonding: experimental and ab initio analyses of vibrational circular dichroism spectra of methyl lactate in water. , 2007, Physical chemistry chemical physics : PCCP.

[39]  T. Swager,et al.  Probing a conjugated polymer's transfer of organization-dependent properties from solutions to films. , 2006, Journal of the American Chemical Society.

[40]  T. Buffeteau,et al.  Vibrational circular dichroism and ab initio structure elucidation of an aromatic foldamer. , 2006, Chemical communications.

[41]  E. Giorgio,et al.  Fenchone, camphor, 2-methylenefenchone and 2-methylenecamphor: a vibrational circular dichroism study. , 2006, The journal of physical chemistry. A.

[42]  P. Bouř,et al.  Vibrational Circular Dichroism of 1,1‘-Binaphthyl Derivatives: Experimental and Theoretical Study , 2001 .

[43]  Stefan Grimme,et al.  Circular Dichroism of Helicenes Investigated by Time-Dependent Density Functional Theory , 2000 .

[44]  R. Janssen,et al.  CIRCULARLY POLARIZED ELECTROLUMINESCENCE FROM A POLYMER LIGHT-EMITTING DIODE , 1997 .