Synthesis, Photophysics and Nonlinear Optical Properties of Stilbenoid Pyrimidine‐Based Dyes Bearing Methylenepyran Donor Groups

Abstract

Arnaud Spangenberg, et al.. Synthesis, photophysics and nonlinear optical properties of stilbenoid pyrimidine-based dyes bearing methylenepyran donor groups.. ChemPhysChem, Wiley-VCH Verlag, 2013, 14 (12), pp.2725-36. 10.1002 Synthesis, Photophysics and Non-linear Optical Properties of Stilbenoid Pyrimidinebased Dyes bearing Methylenepyran Donor GroupsSylvain Achelle,* [a] Jean-Pierre Malval,* [b] Stéphane Aloïse, [c] Alberto Barsella, [d] Arnaud Spangenberg, [b] Loic Mager, [d] Huriye Akdas-Kilig, [e] Jean-Luc Fillaut, [e] Bertrand Caro, [a] and Françoise Robin-le Guen [a] [ AbstractThe nonlinear properties and the photophysical behavior of two π-conjugated chromophores incorporating an electron-deficient pyrimidine core (A) and -methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed when increasing the dimensionality, the NLO response of this series is moderate when considering the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was assigned to a disruption of the electronic conjugation within the dyes scaffold whose geometry deviates from planarity due to a noticeable twisting of the pyranylidene end-groups. This latter structural parameter has also a strong influence on the excited-state dynamics which leads to a very efficient fluorescence quenching.

Photoluminescence Properties of Aryl‐, Arylvinyl‐, and Arylethynylpyrimidine Derivatives

“…Ground state optimized geometries of 158 and 196 were found to be not completely planar with out‐of‐plane twist angles of less than 10° and sizable bond length alternations in the vinyl unit ,. DFT optimized geometry of 202 indicates that the styrylpyrimidine fragment also adopts a quasi‐planar conformation although a torsion angle of approximately 28° is observed with the pyranylidene fragment …”

Incorporation of a ferrocene unit in the π-conjugated structure of donor-linker-acceptor (D-π-A) chromophores for nonlinear optics (NLO)

“…[10][11][12][13][14][15] properties are directly related to the intramolecular charge transfer (ICT) occurring in such structures and can be easily tuned by varying the nature of the donor/acceptor couple and the π-conjugated spacer. [16][17][18] In our group, we have recently optimized the NLO properties of chromophores based on pyrimidine [19][20][21][22][23][24] and/or pyranylidene [22][23][24][25][26][27] moieties as electron-withdrawing and electrondonating fragments respectively. It has been shown that pyrimidine and methylated pyrimidinium salts exhibit higher electron-withdrawing character than well-known pyridine analogues.…”

Synthesis, Photophysical and Redox Properties of the D–π–A Type Pyrimidine Dyes Bearing the 9-Phenyl-9H-Carbazole Moiety

“…In particular, numerous aryl substituted pyrimidines have been studied as fluorescent dyes [23][24][25]. Moreover, it should be noted that arylvinyl pyrimidines are now considered as well established structures of two-photon absorption dyes [26][27][28]. Some pyrimidine derivatives exhibit also the second order nonlinear optical properties [28][29][30][31].…”