Novel boron quadrupolar NLO-phores: optimization of TPA/transparency trade-off via molecular engineering

Molecular two-photon absorption (TPA) has attracted a lot of interest over recent years due to the many applications it offers both in biological imaging and in material science, constantly needing new optimized molecules with large TPA cross-sections. Various structures and functional groups have been studied; however, the use of electron-withdrawing boron groups has not been fully examined yet. As such compounds are known to lead to interesting photoluminescence and nonlinear optical (NLO) properties, we have investigated the TPA properties of a novel series of A-π-A quadrupoles, based on dimesitylborons as acceptor end-groups. Our experimental study reveals that intramolecular charge transfer is a crucial point in these TPA fluorophores, and can be modulated via changing the planarity of the molecule. We have obtained such planar molecules using vinylene spacers, which can release the steric hindrance close to the dimesitylboron end-group. The series of NLO-phores described here is promising for optical power limiting, with excellent TPA/transparency trade-off, and the work has highlighted that perfluorophenylene could be a key component for the future of TPA.

[1]  Guibao Xu,et al.  Blue two-photon excited fluorescence of several D-π-D, A-π-A, and D-π-A compounds featuring dimesitylboryl acceptor , 2004 .

[2]  David J. Hagan,et al.  New Two-Photon Absorbing Fluorene Derivatives: Synthesis and Nonlinear Optical Characterization , 1999 .

[3]  W. Webb,et al.  Design of organic molecules with large two-photon absorption cross sections. , 1998, Science.

[4]  J. H. Malpert,et al.  Effect of Aromatic Ring Substitution on the Optical Properties, Emission Dynamics, and Solid-State Behavior of Fluorinated Oligophenylenevinylenes , 1999 .

[5]  Laurent Vivien,et al.  Broadband optical limiting optimization by combination of carbon nanotubes and two-photon absorbing chromophores in liquids , 2003, SPIE Optics + Photonics.

[6]  Paras N. Prasad,et al.  Highly Active Two-Photon Dyes: Design, Synthesis, and Characterization toward Application , 1998 .

[7]  W. Webb,et al.  Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm , 1996 .

[8]  J. Demas,et al.  Measurement of photoluminescence quantum yields. Review , 1971 .

[9]  Wen-tao Yu,et al.  Trivalent boron as acceptor in D-pi-A chromophores: synthesis, structure and fluorescence following single- and two-photon excitation. , 2002, Chemical communications.

[10]  Jerome Mertz,et al.  Optimization of quadrupolar chromophores for molecular two-photon absorption , 2002 .

[11]  Sankaran Thayumanavan,et al.  Structure−Property Relationships for Two-Photon Absorbing Chromophores: Bis-Donor Diphenylpolyene and Bis(styryl)benzene Derivatives , 2000 .

[12]  Jerome Mertz,et al.  Nanoscale Push-Push Dihydrophenanthrene Derivatives as Novel Fluorophores for Two-Photon-Excited Fluorescence. , 2001, Angewandte Chemie.

[13]  D. Naae.  Biphenyl–perfluorobiphenyl; 1:1 molecular complex , 1979 .

[14]  Zhi-qiang Liu,et al.  Trivalent boron as an acceptor in donor-pi-acceptor-type compounds for single- and two-photon excited fluorescence. , 2003, Chemistry.

[15]  Débora T. Balogh,et al.  Two-photon absorption in azoaromatic compounds , 2002 .

[16]  M. Blanchard‐Desce,et al.  Towards "smart" multiphoton fluorophores: strongly solvatochromic probes for two-photon sensing of micropolarity. , 2005, Chemical communications.

[17]  Soo Young Park,et al.  Triphenylamine-Cored Bifunctional Organic Molecules for Two-Photon Absorption and Photorefraction , 2004 .

[18]  B. Strehmel,et al.  The Influence of σ and π Acceptors on Two‐Photon Absorption and Solvatochromism of Dipolar and Quadrupolar Unsaturated Organic Compounds , 2003 .

[19]  Jerome Mertz,et al.  New quadrupolar fluorophores with high two-photon excited fluorescence , 1999 .

[20]  W. Rettig,et al.  Fluorescence Probes Based on Twisted Intramolecular Charge Transfer (TICT) States and Other Adiabatic Photoreactions , 2002 .

[21]  W. Webb,et al.  Two-Photon Fluorescence Excitation Cross Sections of Biomolecular Probes from 690 to 960 nm. , 1998, Applied optics.

[22]  N. Taylor,et al.  Third‐order Nonlinear Optical Properties of Organoboron Compounds: Molecular Structures and Second Hyperpolarizabilities , 1996 .

[23]  L. Jullien,et al.  Diaroyl(methanato)boron difluoride compounds as medium-sensitive two-photon fluorescent probes. , 2004, Chemistry.

[24]  Paras N. Prasad,et al.  Degenerate nonlinear absorption and optical power limiting properties of asymmetrically substituted stilbenoid chromophores , 2004 .

[25]  Seth R. Marder,et al.  Bis(dioxaborine) compounds with large two-photon cross sections, and their use in the photodeposition of silver , 2003 .

[26]  Ian D. Williams,et al.  Three coordinate phosphorus and boron as π-donor and π-acceptor moieties respectively, in conjugated organic molecules for nonlinear optics: crystal and molecular structures of E-Ph–CHCH–B(mes)2, E-4-MeO–C6H4–CHCH-B(mes)2, and E-Ph2P–CHCH–B(mes)2[mes = 2,4,6-Me3C6H2] , 1990 .

[27]  J. Perry,et al.  Ultrabright supramolecular beacons based on the self-assembly of two-photon chromophores on metal nanoparticles. , 2003, Journal of the American Chemical Society.

[28]  Guibao Xu,et al.  Triaryl boron-based A-pi-A vs triaryl nitrogen-based D-pi-D quadrupolar compounds for single- and two-photon excited fluorescence. , 2004, Organic letters.

[29]  Xiaopeng Wang,et al.  A chemically labeled cytotoxic agent: two-photon fluorophore for optical tracking of cellular pathway in chemotherapy. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[30]  Mireille Blanchard-Desce,et al.  Molecular engineering of push–pull dipolar and quadrupolar molecules for two-photon absorption: A multivalence-bond states approach , 2000 .

[31]  N. Taylor,et al.  Linear and nonlinear optical properties of three-coordinate organoboron compounds , 2000 .

[32]  Polymers and oligomers with transverse aromatic groups and tightly controlled chain conformations , 1998 .

[33]  Claudine Katan,et al.  Enhanced two-photon absorption with novel octupolar propeller-shaped fluorophores derived from triphenylamine. , 2004, Organic letters.

[34]  Jerome Mertz,et al.  Synthesis and photophysical properties of new conjugated fluorophores designed for two-photon-excited fluorescence. , 2002, Organic letters.

[35]  Christopher D. Entwistle,et al.  Investigation of two-photon absorption behavior in symmetrical acceptor-pi-acceptor derivatives with dimesitylboryl end-groups. Evidence of new engineering routes for TPA/transparency trade-off optimization. , 2005, Physical chemistry chemical physics : PCCP.