Self‐assembly of an acentric co‐crystal of a highly hyperpolarizable merocyanine dye with optimized alignment for nonlinear optics
Source abstract
Abstract
Non‐centrosymmetric arrangement of the chromophores is a prerequisite for non‐vanishing macroscopic second‐order nonlinear optical responses. It is shown that an acentric packing of a highly polarizable merocyanine dye, with optimized orientation for frequency conversions, can be induced by hydrogen‐bond‐directed self‐assembly with appropriate phenolic derivatives. The highly polar co‐crystal is demonstrated to have potential for both second‐ and third‐order nonlinear optics applications owing to its large nonlinear response and favorable crystal properties.
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Research context
OpenAlex topics: Nonlinear Optical Materials Research · Crystallography and molecular interactions · Molecular spectroscopy and chirality
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References (28)
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26. The melting point is the peak temperature of the melting curve determined by differential scanning calorimetry using a heating rate of 2 K min−1. The melting point of crystals prepared from 2 and 3 is 186°C and the melting point of crystals prepared from 2 and 4 is 193°C.
27. 1H NMR (300 MHz CD3OD 25°C TMS) δ 2.45 (s 3H: CH3) 3.95 (t.3J(H.H) = 4.9 Hz. 2H: CH2). 4.49 (t.3J(H.H) = 4.8 Hz. 2H: CH2). 6.06 (s. 1H: ArH ). 6.22 (d.3J(H.H) = 8.9 Hz. 1H. ArH ) 6.74(d3J(H.H)= 8.4 Hz 2H: ArH). 7.06 (d.3J(H.H) = 16 Hz. 1H: CH). 7. = 54 (d.3J(l 1.1‐1) = 8.7 Hz. 1 H. ArH ). 7.57 (d.3J (H.H) = 9.2 Hz. 2H; ArH ). 7.83 (d.3J(H.H) = 15.9 Hz. 1H: CH). 7.96 (d.3J(H.H) = 5.8 Hz. 2H: ArH). 8.53 (d.3J(H H) = 6.0 Hz. 2H: ArH). Elemental analysis for C23 H23NO5(M.W = 393.44): Found (Calc%): C = 70.03 (70.21). H = 6.01 (5.89). N = 3.57 (3.56).
28. Crystal data for C23H23NO5: monoclinic. Pc: u = 7.914(11). b = 11.24(2). c = 11.44(2) Å. b = 106.14 (12)°. ν= 978(3)Å3Z=2.rcalcd=1.337 gcm−3. T = 293 K. Syntex P21 diffractometer (MoKα. λ = 0.71073 Ǎ). 1441 measured reflections within 3° < 2θ < 45° of which 1362 arc independ ent. 1218 with F > 4.0σ(F). The structure was solved by directed methods and all heavy. Atoms were refined by full matrix least squares procedures with 275 parameters. All H atoms were located according to the riding model with fixed isotropic U except the hydrogen bonded H. which were taken from a difference Fourier synthesis and refined iso tropically. R = 0.0339. wR = 0.0409. W−− σ2=(F). 0.0010F2. GOF = 1.10. residual electron density 0.13/‐0.14 eÅ−3. Of the two space groups P2/c and Pc consistent with the crystallographic data set. Pc was strongly favored from the intensity statistics. The non‐centrosymmetric space group Pc was finally confirmed by the successful structure refinement in complete agreement with the observed optical properties.