Synthesis and properties of a second‐order nonlinear optical side‐chain polyimide

A thermal stable aromatic polyimide (PI) with side‐chain second‐order nonlinear optical (NLO) chromophores has been developed. The PI was prepared by the ring‐opening polyaddition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride with a new diamine having two N‐ethyl‐N‐[4‐[(6‐chlorobenzothiazol‐2‐yl)diazenyl]phenyl]‐2‐aminoethanol units as the NLO chromophore, followed by poling during or after the thermal imidization process. The resulting PI had number and weight‐average molecular weights (M_n, M_w) of 25,000 and 80,000, respectively, and a relatively high glass transition temperature of 180°C. The second harmonic coefficient (d₃₃) of PI at the wavelength of 1.064 μm was 138 pm/V (329.6 × 10⁻⁹ esu) and remained unchanged at elevated temperatures. The corona poling process of the NLO‐substituted poly(amic acid) to the PI was also studied in detail by measuring the second harmonic generation (SHG) from the polymer films. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1321–1329, 1999     

Synthesis of ladder polymers containing polydiacetylene backbones connected with methylene chains and their optical properties

The polymers consisting of polydiacetylene (PDA) backbones were obtained from the novel monomer derivatives, R CC CC R′ CC CC R [where R =  (CH₂)₄OCONHCH₂COOC₄H₉, R′ =  (CH₂)_n ; n = 2, 4, 8] [4BCMU4A(n)], in which linear methylene chain is sandwiched between two diacetylene moieties by solid-state 1,4-addition reaction. The polymerization process was investigated in detail by using spectroscopic techniques such as solid-state ¹³C-NMR, visible absorption, and IR absorption spectra. It was estimated that the polymerization of 4BCMU4A(8) and 4BCMU4A(4) takes place by two consecutive 1,4-addition reactions to form two PDA backbones, which constitute the two poles of the respective ladders. The bridging methylene chain length in the monomer was found to play a vital role as far as the polymerization process is concerned. Thus, the monomers with eight or four methylene units could form the ladder–PDAs by a two-step process, whereas the monomer containing two methylene units could only undergo one-step of 1,4-addition reaction. Further, it was found that the crystallinity of the polymers depends on the methylene chain length in the monomers, 4BCMU4A(8) being the most crystalline of all. These structural features strongly affect their absorption spectra. The third-order nonlinear optical susceptibilities (χ⁽³⁾) for these polymers were measured using third-harmonic generation method. The largest χ⁽³⁾ value obtained was 3.4 × 10⁻¹¹ esu for the poly[4BCMU4A(8)] thin film in resonant region. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3537–3548, 1999     

Adaptive approach for nonlinear sensitivity analysis of reaction kinetics

We present a unified approach for linear and nonlinear sensitivity analysis for models of reaction kinetics that are stated in terms of systems of ordinary differential equations (ODEs). The approach is based on the reformulation of the ODE problem as a density transport problem described by a Fokker-Planck equation. The resulting multidimensional partial differential equation is herein solved by extending the TRAIL algorithm originally introduced by Horenko and Weiser in the context of molecular dynamics (J. Comp. Chem. 2003, 24, 1921) and discussed it in comparison with Monte Carlo techniques. The extended TRAIL approach is fully adaptive and easily allows to study the influence of nonlinear dynamical effects. We illustrate the scheme in application to an enzyme-substrate model problem for sensitivity analysis w.r.t. to initial concentrations and parameter values.     

The first metal (Nd3+, Mn2+, and Pb2+) coordination compounds of 3,5-dinitrotyrosine and their nonlinear optical properties

The reactions of 3,5-dinitrotyrosine (H2DNTY) with Nd(NO3)3.6H2O, Mn(ClO4)2.6H2O, and Pb(OAc)2 afforded three homochiral compounds: discrete [Nd(Hdnty)2(NO3)(H2O)5].3H2O (1) and two- and three-dimensional coordination polymers, [Mn(Hdnty)2] (2) and [Pb(dnty)(0.5 H2O)] (3), respectively. The Nd atom in 1 displays a tricapped trigonal prism and supramolecular weak interactions, such as pi-pi stacking and H-bonds, between amino and nitro groups result in the formation of a three-dimensional network through these interactions. 2 has a two-dimensional square-grid topological net while 3 has the first three-dimensional homochiral ThSi2 net. To the best of our knowledge, these are the first metal coordination compounds with 3,5-dinitrotyrosine. Preliminary second harmonic generation (SHG) investigations indicated that 1 and 2 are SHG active with estimated responses 5 and 6 times larger than that of urea, respectively, while 3 is SHG non-active (obeying the Klainman symmetry requirement). Strong enhancement of their SHG efficiency, compared with H2DNTY, may be due to 1) the addition of a good donor-pi-acceptor organic chromophore into the compound resulting in superior qualities of both inorganic and organic materials and 2) the H-bonds that persist in them. Crystal data: 1: C18H32N7O25Nd, Mr = 890.75 g mol(-1), monoclinic, P2(1), a=7.0179(7), b=27.060(3), c=8.3097(8) A, alpha=gamma=90.00, beta=95.646(2) degrees , V=1570.4(3) A(3), Z=2, rho(calcd)=1.884 Mg m(-3), R(1)=0.0489, wR(2)=0.1223, mu=17.67 mm(-1), S=0.811, Flack value=0.003(13); 2: C(18)H(16)N(6)O(14)Mn, M(r)=595.31 g mol(-1), orthorhombic, P2(1)2(1)2, a=8.4381(14), b=13.639(2), c=19.697(3) A, alpha=beta=gamma=90.00 degrees , V=2266.9(6) A(3), Z=4, rho(calcd)=1.744 Mg m(-3), R(1)=0.0866, wR(2)=0.2030, mu=6.72 mm(-1), S=1.095, Flack value=0.02(6); 3: C(9)H(8)N(3)O(7.5)Pb, M(r)=485.37 g mol(-1), tetragonal, P4(1)2(1)2, a=12.8136(12), b=12.8136(12), c=14.931(2), alpha=beta=gamma=90.00 degrees , V=2451.5(5) A(3), Z=8, rho(calcd)=1.885 Mg m(-3), R(1)=0.0564, wR(2)=0.1323, mu=6.942 mm(-1), S=0.878, Flack value=0.03(2). For space group P4(3)2(1)2: R(1)=0.0672, wR(2)=0.1656, S=1.034, Flack value=1.02(3); this suggests the chosen space group P4(1)2(1)2 is correct.     

偶氮苯取代乙炔功能化合物的合成与表征

采用偶氮偶联和金属钯催化偶联反应法,合成了一系列非线性光学基团直接取代乙炔化合物,其结构经^1HNMR,IR,DSC及元素分析等表征。     

Determination of molecular orientation distribution of a stable paramagnetic probe in oriented 4-cyano-4’-<Emphasis Type="Italic">n</Emphasis>-pentylbiphenyl

The molecular orientation distribution function of a stable radical 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in magnetic-field oriented 4-cyano-4’-n-pentylbiphenyl was determined from the angular dependence of the ESR spectra. The preferred molecular orientation of radical species in the liquid crystal matrix was determined. The temperature evolution of the orientation distribution function was studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 2005.     

反应NH~4ClO~4+Mg+K~2Cr~2O~7的非线性化学动力学1: 固相振 荡燃烧的实验现 象

在外界环境条件恒定的情况下,反应体系NH~4ClO~4+Mg+K~2Cr~2O~7的燃烧过程是不均匀的,燃烧和光强呈周期性的强弱变化,给出了典型的化学振荡现象。本文介绍了NH~4ClO~4+Mg+K~2Cr~2O~7体系的固相振荡燃烧配方,对新配方进行了实验,研究了这个体系的固相振荡燃烧现象的非线性特性,分析了固相化学振荡的非线性化学反应动力学机理。     

钨磷酸［C2H10NO］3［PW12O40］CH3CN电荷转移盐的合成、表征、光色性及非线性光学性质

杂多化合物为一类重要的多核配合物,因其优良的催化性能及其在其他领域的应用前景而受到广泛的重视［１－３］。研究发现,Ｋｅｇｇｉｎ型阴离子具有很强的接受电子能力［４］,可作为电子受体与有机给体相结合形成电荷转移盐,该类盐在光激发下可以发生电荷转移,从而表...     

H4GeMo12-nWnO40·mH2O（n=0, 9, 11, 12)和N-甲基吡咯烷酮电荷转移盐的合成、表征和非线性光学性质研究

由Ｈ４ＧｅＭｏ１２－ｎＷｎＯ４０·ｍ Ｈ２Ｏ（ｎ＝ ０, ９, １１, １２）和Ｎ－甲基吡咯烷酮合成,随后在ＣＨ３ＣＮ 和水中结晶,制成了一系列分子组成为［ＮＭＰＨ］４ＧｅＭｏ１２－ｎＷｎＯ４０·ＣＨ３ＣＮ的电荷转移化合物。并用元素分析、红外光谱、电子光谱进行了表征。结果表明在该系列化合物中, Ｎ－甲基吡咯烷酮通过Ｎ原子与酸中的质子结合成阳离子而与阴离子成盐;固体中阴离子和阳离子之间存在强的相互作用;化合物在光照下发生分子内电荷转移, 导致阳离子的氧化和阴离子的还原;ＥＳＲ结果表明阴离子还原反应处于单电子阶段; 非线性光学性质研究表明, 随着化合物分子内钨取代数的增多, 化合物倍频效应增强,三阶非线性系数增大