• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    雙核釕-DMBA雙芳香炔化合物的合成和電化學(xué)性質(zhì)

    2017-11-13 12:22:07SusannahBanzigerEileenJudkinsMatthiasZeller
    無機(jī)化學(xué)學(xué)報 2017年11期
    關(guān)鍵詞:異丙基酰亞胺雙核

    Susannah D.Banziger Eileen C.Judkins Matthias Zeller 任 彤

    (Department of Chemistry,Purdue University,West Lafayette,Indiana 47907,USA)

    雙核釕-DMBA雙芳香炔化合物的合成和電化學(xué)性質(zhì)

    Susannah D.Banziger Eileen C.Judkins Matthias Zeller 任 彤*

    (Department of Chemistry,Purdue University,West Lafayette,Indiana 47907,USA)

    摘要: 在弱堿性條件下,雙核釕(Ⅲ)配合物 Ru2(DMBA)4(NO3)2(DMBA=tetrakis-N,N′-dimethylbenzamidinate)與不同芳香炔反應(yīng)(其中芳香基團(tuán)包括:NAPme,N-甲基-1,8-萘二甲酰亞胺;NAPiso,N-異丙基-1,8-萘二甲酰亞胺;Naphth,萘;Ant,蒽),制備了相應(yīng)的端基炔取代配合物 trans-Ru2(DMBA)4(C2Ar)2(Ar=NAPme,1;NAPiso,2;Naphth,3;Ant,4)。 利用 X 射線晶體衍射測定了它們的結(jié)構(gòu)。 所有化合物的Ru-Ru鍵長處于單鍵范圍(0.245 0~0.249 1 nm),它們均是抗磁性物質(zhì)。進(jìn)一步通過1H NMR和UV-Vis-NIR光譜進(jìn)行了表征。電化學(xué)研究表明,所有化合物顯示出與芳香基團(tuán)有關(guān)的2個可逆的單電子氧化還原過程(包括一個氧化過程和一個還原過程)。

    雙核釕;炔基;1,8-萘二甲酰亞胺;萘基;蒽基

    0 Introduction

    Conjugated metal-alkynylcompounds are of interest to both the inorganic and materials chemistry communities[1-3]and have been studied as prototypical molecular wires[4-7],light emitting materials[8-9]and photovoltaic materials[10].Recent interesting examples of linearly conjugated metal alkynyl or metal alkenyl species include those based on mono-and bimetallic Ru compounds supported by phosphine[11-14]and PtAu2heterometallics[15-16].

    Diruthenium compounds bearing axial alkynyl ligands are known for their capacity to undergo multiple reversible one-electron oxidation/reduction[2],strongly couple across oligoyn-diyl bridges[17-19],mediate couplings between two ferrocenyls[20],facilitate the formation of supramolecules[21-22],and function as the active species in molecular devices[23-24].Among N,N′-bidentate ligands used to support the Ru2core,DMBA(N,N′-dimethylbenzamidinate)and its derivatives are the most electron donating and support a variety of Ru2(Ⅲ,Ⅲ)bis-alkynyls[25-27]and Fe-Ru2heterometallic complexes[28].Reported in this contribution are four new trans-Ru2(DMBA)4(C2Ar)2type compounds with Ar as 4-N-methyl-1,8-naphthalimide (1),4-N-isopropyl-1,8-naphthalimide (2),1-naphthalene (3)and 9-anthracene(4),as sketched in Scheme 1.

    1 Experimental

    1.1 Materials and measurements

    [Ru2(DMBA)4(NO3)]wasprepared according to literature procedures[29].Also prepared according literature procedures were 1-ethynylnaphthalene[30],9-ethynylanthracene[31],and 4-ethynyl-N-methyl-1,8-naphthalimide[32].THF was distilled over Na/benzophenone under a N2atmosphere.Diisopropylamine was purchased from Acros Organics and distilled over potassium hydroxide.The synthesis of Ru2compoundswas performed underambientatmosphere.Allother reactions were carried out using Schlenk techniques under N2.UV-Vis-NIR spectra were obtained with a JASCO V-670 UV-Vis-NIR spectrophotometer.Infrared spectra were obtained on a JASCO FT-IR 6300 spectrometer via ATR on a ZnSe crystal.1H NMR spectra were recorded on a Varian MERCURY300 NMR.Cyclic voltammograms were recorded in 0.1 mol·L-1n-Bu4NPF6and 1.0 mmol·L-1ruthenium species solution (THF,Ar degassed)using a CHI620A voltammetric analyzerwith aglassycarbon workingelectrode(Diameter=2 mm),Pt-wire counter electrode,and an Ag/AgCl reference electrode with ferrocene used as an internal reference.

    1.2 Preparation of 4-Ethynyl-N-isopropyl-1,8-naphthalimide and its precursors

    4-Bromo-1,8-naphthalic anhydride (1.00 g,3.61 mmol)and isopropylamine (1.00 mL,11.66 mmol)were added to degassed ethanol (30 mL).The mixture was refluxed under nitrogen for 18 hours to yield a dark yellow solution and then placed in an ice bath.A light yellow precipitate formed which was then filtered,and rinsed with methanol(30 mL)to afford 0.89 g of 4-bromo-N-isopropyl-1,8-naphthalimide (77%based on 4-bromo-1,8-naphthalic anhydride).1H NMR (CD3OD):δ 8.64 (dd,J=7.3,1.1 Hz,1H),8.55 (dd,J=8.5,1.1 Hz,1H),8.40 (d,J=7.9 Hz,1H),8.03 (d,J=7.9 Hz,1H),7.84 (dd,J=8.5,7.4 Hz,1H),5.42 (hept,J=7.0 Hz,1H),1.60 (d,J=7.0 Hz,6H).IR (cm-1):C=O:1 656 (s),1 700 (s).

    4-Bromo-N-isopropyl-1,8-naphthalimide (890 mg,2.80 mmol),Pd(PPh3)2Cl2(40 mg,0.057 mmol)and CuI (11 mg,0.058 mmol)were dried under vacuum for 3 hours,upon which 35 mL of diisopropylamine and ethynyltrimethylsilane (0.8 mL,5.78 mmol)were added.The dark brown solution was allowed to stir at room temperature for 30 minutes and then heated to reflux for 30 minutes until the solvent became black.Upon rotary evaporation,the off-white solid was redissolved in EtOAc,rinsed through a short silica plug,and purified by column chromatography (SiO2,VCH2Cl2/Vhexanes=1)to afford 855 mg of 4-ethynyltrimethylsilyl-N-isopropyl-1,8-naphthalimide (91% based on 4-bromo-N-isopropyl-1,8-naphthalimide).Desilylation of 4-ethynyltrimethylsilyl-N-isopropyl-1,8-naphthalimide(675 mg,2.01 mmol)was accomplished using K2CO3in a MeOH/CH2Cl2(2∶1,V/V)solution to afford 524 mg of 4-ethynyl-N-isopropyl-1,8-naphthalimide (98%).1H NMR (CD3OD):δ 8.63 (dd,J=8.6 Hz,2H),8.51 (d,J=7.5 Hz,1H),7.93 (d,J=7.7 Hz,1H),7.82 (t,J=7.9 Hz,1H),5.43 (hept,1H),3.72 (s,1H),1.60 (dd,J=7.0,0.6 Hz,6H).Visible spectra,λmax/nm (ε /(L·mol-1·cm-1):350 (35 240),366 (32 580).IR (cm-1):C=O:1653 (s),1700 (s);C≡C:2102 (m);C≡C-H:3 227 (s).

    1.3 Preparation of 1

    Ru2(DMBA)4(NO3)2(45.2 mg,0.049 mmol),4-ethynyl-N-methyl-1,8-naphthalimide (70.1 mg,0.298 mmol),and Et3N (0.6 mL)were dissolved in 50 mL THF and reacted for 4 h to yield a dark red solution.Upon solvent removal,the residue was purified by column chromatography (SiO2,Vhexanes/VTHF=9).Unreacted ligand eluted first,followed closely by the desired product as a deep red band.Upon solvent removal,the red fraction was recrystallized from hexanes-THF to afford 43.7 mg of 1 (70%based on Ru).ESI-MS(m/z): [M]+,1 260.0.1H NMR (CD3OD):δ 8.82 (d,J=8.2 Hz,2H),8.54 (d,J=7.4 Hz,2H),8.43 (d,J=7.8 Hz,2H),7.60(d,J=7.8 Hz,2H),7.53~7.46 (m,12H),7.41 (d,J=7.8 Hz,2H),7.07 (d,J=7.1 Hz,8H),3.53 (s,6H),3.40 (s,24H).Visible spectra,λmax/nm (ε /(L·mol-1·cm-1):322(16 160),460 (15 200),550 (28 200),877 (1 690).IR(cm-1):C=O:1 654 (s),1 691 (s);C≡C:2 047 (s).Anal.Found (Calcd.)for C70H68N10O5Ru2(1·THF,%):C,63.28 (63.14);H,5.04 (5.14);N,10.52 (10.52).

    1.4 Preparation of 2

    Ru2(DMBA)4(NO3)2(93mg,0.102mmol),4-ethynyl-N-isopropyl-1,8-naphthalimide (134 mg,0.508 mmol)and Et3N (0.3 mL)were reacted in 100 mL of THF for 3 h.The reaction mixture was purified similarly to that of 1 to afford 112 mg of 2 (84%based on Ru).ESI-MS(m/z): [M]+,1 316.1.1H NMR (CD3OD): δ 8.78(dd,J=8.3,1.3 Hz,2H),8.50 (dt,J=7.3,1.6 Hz,2H),8.40 (dd,J=7.8,1.8 Hz,2H),7.74~7.27 (m,16H),7.10~7.02 (m,8H),5.47~5.34 (m,2H),3.40 (d,J=1.8 Hz,24H),1.57 (dd,J=3.1,1.9 Hz,12H).Visible spectra,λmax/nm (ε /(L·mol-1·cm-1):323 (20 940),462 (20 050),549 (37 140),870 (2 450).IR (cm-1):C=O:1 653 (s),1 690 (s);C≡C:2 049 (s).Anal.Found (Calcd.)for C74H80N10O7Ru2(2·THF·2H2O,%):C,62.31 (62.43);H,5.40 (5.66);N,9.82 (9.83).

    1.5 Preparation of 3

    Ru2(DMBA)4(NO3)2(0.095 g,0.104 mmol)was added to a solution of 1-ethynylnaphthalene (0.043 g,0.28 mmol)and 3 mL Et3N in THF (30 mL)and stirred for 4 h.The crude solution was run over a silica plug,eluting 3 with a solvent mixture with Vhexanes∶VEtOAc∶VTHF=89∶10∶1.The ensuing recrystallization from THF/MeOH yielded 3 as deep red,crystalline solid (52 mg,0.048 mmol,46%based on Ru).ESI-MS(m/z):[M+H]+,1094.1H NMR (CDCl3): δ 8.59 (dd,J=7.9,1.4 Hz,2H),7.71 (dd,J=6.9,1.3 Hz,2H),7.51~7.32 (m,22H),7.10~7.03 (m,8H),3.42 (s,24H).Visible spectra,λmax/nm (ε /(L·mol-1·cm-1):372sh (32 162),391 (33 184),508 (18 195),681sh (1 791),892 (3 214).IR (cm-1):C ≡C:2 063 (s).Anal.Found (Calcd.)for C60H60N8O1Ru2(3·H2O,%):C,64.85 (64.85);H,5.64(5.44);N,9.97 (10.08).

    1.6 Preparation of 4

    Ru2(DMBA)4(NO3)2(0.085 g,0.093 mmol)was added to a solution of 9-ethynylanthracene (0.055 g,0.27 mmol)and 1.5 mL Et2NH in THF (20 mL)and stirred 12 h.The crude solution was purified similarly to that of 3 to afford 50 mg of 4 (0.042 mmol,45%based on Ru).ESI-MS (m/z): [M+H]+,1195.1H NMR(CDCl3): δ 8.88 (d,J=8.4 Hz,4H),7.93 (s,2H),7.86(d,J=8.5 Hz,4H),7.51~7.30 (m,20H),7.13 (d,J=6.8 Hz,8H),3.55 (s,24H).Visible spectra,λmax/nm (ε /(L·mol-1·cm-1):283sh (35 544),289 (49 953),502(41 938),699sh (1 785),903 (2 291).IR (cm-1):C≡C:2045 (s).Anal.Found (Calcd.)for C72H73N8O2.5Ru2(4·1.5H2O·THF,%):C,66.97 (66.91);H,5.76 (5.69);N,8.53 (8.67).

    CCDC:1555598,1;1555599,2;1555609,3;1555611,4.

    2 Results and discussion

    2.1 Syntheses

    As shown in Scheme 1,compounds 1~4 were prepared from the direct reaction between Ru2(DMBA)4(NO3)2[29]and HC2Ar in the presence of Et3N/Et2NH in satisfactory to very good yields after purification.Consistentwith the previous studies ofrelated compounds,compounds 1~4 are diamagnetic,which facilitate their characterization using1H NMR.In addition,the purity of these compounds was also confirmed by combustion analysis.

    2.2 Crystal structures

    Molecularstructuresofcompounds 1~4 have been determined using single crystal X-ray diffraction and structural plots are shown in Fig.1.While molecules 2~4 do not contain a crystallographic symmetry element,there is a C2axis passing through the midpoint of the Ru-Ru bond and relating two adjacent DMBA ligands in 1.It is clear from Fig.1 that all compounds adopt the expected paddlewheel geometry with four equatorial bridging DMBA and two axial arylethynyl ligands.The Ru-Ru bond lengths are within a narrow range of 0.245 0~0.249 1 nm,which agrees with the values reported for other Ru2(DMBA)4(C2R)2type compounds[2]and is consistent with the presence of a Ru-Ru single bond.The Ru-C bond lengths in 1~4 (0.196~0.201 nm)are also in agreement with the previous reports[2,33].

    A notable structural feature of the Ru2(DMBA)4(C2Ar)2type compounds is the significant distortion of the first coordination sphere of the Ru2core from an idealized paddlewheel structure (D4h).The origin of such distortion is rooted in a second order Jahn-Teller effect,as originally proposed to rationalize the structures of the Ru2(DArF)4(C2Ph)2type compounds (DArF=N,N′-diarylformamidinate)[34].The structural distortion is typically reflected by (i)the large variation in Ru-N bond lengths, (ii)both acute and obtuse Ru-Ru-N angles,and (iii)significantly nonlinear Ru-Ru-C angles.These are clearly the case for the structures of 1~3.However,the distortion is completely suppressed in 4:Ru-N bond lengths are within a narrow range,Ru-Ru-N angles are all acute and Ru-Ru-C angles are fairly linear.We surmise that the steric effect of anthracene may be responsible for a more symmetric structure.

    Fig.1 ORTEP plots of compounds 1 (a),2 (b),3 (c)and 4 (d)at 30%probability level

    Table 1 Selected bond lengths (nm)and angles (°)for compounds 1~4*

    Continued Table 1

    2.3 Vis-NIR spectroscopy and voltammetry

    As noted earlier,all four compounds have a deep wine red color with a slight variation in hue.The Vis-NIR absorption spectra of 1~4 are shown in Fig.2,featuring a distinctive NIR band around ca.880 nm that is responsible for the wine red color.This absorption is likely attributed to the π*(Ru2)→δ*(Ru2)transition according to a prior TD-DFT analysis of related Ru2(DMBA)4(C2R)2compounds[20].TheVis region is dominated by a very intense band with a transition energy depending on the nature of Ar.While the λmaxfor Ar as both NAPme(1)and NAPiso(2)are 550 nm,the λmaxfor Ar as Naphth (3)and Ant (4)are blue-shifted to 508 and 502 nm,respectively.This absorption may be assigned to the δ(Ru2)+π(C≡C)→σ*(Ru-C)transition based on the said TD-DFT study,which provides a ready rationale for the observed energy dependence on Ar.Electron donating Naphth and Ant destabilize σ*(Ru-C)more significantly than electron withdrawing NAPmeand NAPiso,which led to significantly wider optical gaps for 3 and 4.The Vis spectra of both 1 and 2 also feature a shoulder at ca.450 nm that is absent in the spectra of 3 and 4,pointing to a possible NAP based transition.Also noteworthy is that while all four aryl ligands are strongly fluorescent,compounds 1~4 are non-emissive,reflecting the efficient quenching by the Ru2(DMBA)4core.

    Fig.2 Vis-NIR spectra of compounds 1~4 recorded in THF solution

    Ru2(DMBA)4(C2R)2type compounds often display rich electrochemical characteristics[20,26-27,33]and compounds 1~4 are no exception.As shown in Fig.3,their cyclic voltammograms (CV)all consist of two reversible one-electron couples,an oxidation (A)and a reduction (B),and both are Ru2-based.It is also clear that the electrode potentials of compounds 1 and 2 are far more positive than those of the corresponding couples in 3 and 4,reflecting the electron-deficient nature of NAP ligands.Since the oxidation and reduction potentials can be respectively correlated with the HOMO and LUMO energies[35-36],the electrochemical HOMO-LUMO gap (Eg)can be directly calculated from the difference between E1/2(A)and E1/2(B),and the values for 1 ~4 are listed in Table 2.Interestingly,the Egremains fairly constant across the series despite the large variance in electrode potentials.Clearly,both the HOMO and LUMO are Ru2-based,and the inductive ligand effects on their energies are about the same within the experimental errors.

    Fig.3 Cyclic voltammograms of compounds 1~4 recorded in 0.10 mol·L-1THF solution of Bu4NBF4at the scan rate of 100 mV·s-1

    Table 2 Electrode potentials of observed redox couples in Ru2(DMBA)4(C2Ar)2

    3 Conclusions

    Four new Ru2(DMBA)4(C2Ar)2compounds have been prepared and structurally characterized.While both the voltammetric responses and electronic absorption spectra are dominated by the Ru2-centered processes,both the electrode potentials and excitation energies exhibitsignificant dependence on the arylethynyl ligands.

    [1]Paul F,Lapinte C.Coord.Chem.Rev.,1998,178-180:431-509

    [2]Ren T.Organometallics,2005,24:4854-4870

    [3]Costuas K,Rigaut S.Dalton Trans.,2011,40:5643-5658

    [4]Blum A S,Ren T,Parish D A,et al.J.Am.Chem.Soc.,2005,127:10010-10011

    [5]Meng F B,Hervault Y M,Norel L,et al.Chem.Sci.,2012,3:3113-3118

    [6]ZHANG Xiang-Yi(張相宜),ZHENG Qi(鄭啟),QIAN Chen-Xi(錢晨熹),et al.Chinese J.Inorg.Chem.(無機(jī)化學(xué)學(xué)報),2011,27:1451-1464

    [7]Wen H M,Yang Y,Zhou X S,et al.Chem.Sci.,2013,4:2471-2477

    [8]Chen Z N,Zhao N,F(xiàn)an Y,et al.Coord.Chem.Rev.,2009,253:1-20

    [9]Yam V W-W.Acc.Chem.Res.,2002,35:555-563

    [10]Wong W Y,Ho C L.Acc.Chem.Res.,2010,43:1246-1256

    [11]Liu S H,Xia H P,Wen T B,et al.Organometallics,2003,22:737-743

    [12]Liu S H,Hu Q Y,Xue P,et al.Organometallics,2005,24:769-772

    [13]Kong D D,Xue L S,Jiang R,et al.Chem.Eur.J.,2015,21:9895-9904

    [14]Ou Y P,Zhang J,Zhang F X,et al.Dalton Trans.,2016,45:6503-6516

    [15]Xu L J,Zeng X C,Wang J Y,et al.ACS Appl.Mater.Interfaces,2016,8:20251-20257

    [16]Zhang L Y,Xu L J,Wang J Y,et al.Dalton Trans.,2017,46:865-874

    [17]Xu G L,Zou G,Ni Y H,et al.J.Am.Chem.Soc.,2003,125:10057-10065

    [18]Cao Z,Xi B,Jodoin D S,et al.J.Am.Chem.Soc.,2014,136:12174-12183

    [19]Wong K T,Lehn J M,Peng S M,et al.Chem.Commun.,2000:2259-2260

    [20]Xu G L,Crutchley R J,DeRosa M C,et al.J.Am.Chem.Soc.,2005,127:13354-13363

    [21]Zuo J L,Herdtweck E,de Biani F F,et al.New J.Chem.,2002,26:889-894

    [22]Zuo J L,Herdtweck E,Kühn F E.Dalton Trans.,2002:1244-1246

    [23]Mahapatro A K,Ying J,Ren T,et al.Nano Lett.,2008,8:2131-2136

    [24]Zhu H,Pookpanratana S J,Bonevich J E,et al.ACS Appl.Mater.Interfaces,2015,7:27306-27313

    [25]Ying J W,Cordova A,Ren T Y,et al.Chem.Eur.J.,2007,13:6874-6882

    [26]Ying J W,Liu I P C,Xi B,et al.Angew.Chem.Int.Ed.,2010,49:954-957

    [27]Cai X M,Zhang X Y,Savchenko J,et al.Organometallics,2012,31:8591-8597

    [28]Wang C F,Zuo J L,Ying J W,et al.Inorg.Chem.,2008,47:9716-9722

    [29]Xu G L,Jablonski C G,Ren T.Inorg.Chim.Acta,2003,343:387-390

    [30]Chang N H,Mori H,Chen X C,et al.Chem.Lett.,2013,42:1257-1259

    [31]Takahashi S,Kuriyama Y,Sonogashira K,et al.Synthesis,1980:627-630

    [32]McAdam C J,Morgan J L,Murray R E,et al.Aust.J.Chem.,2004,57:525-530

    [33]Xu G L,Campana C,Ren T.Inorg.Chem.,2002,41:3521-3527

    [34]Lin C,Ren T,Valente E J,et al.J.Chem.Soc.,Dalton Trans.,1998:571-576

    [35]Ren T.Coord.Chem.Rev.,1998,175:43-58

    [36]Loutfy R O,Loutfy R O.Can.J.Chem.,1976,54:1454-1463

    Diruthenium-DMBA Bis-Alkynyl Compounds with Hetero-and Extended-Aryl Appendant:Preparation and Electrochemical Property

    Susannah D.Banziger Eileen C.Judkins Matthias Zeller Tong Ren*
    (Department of Chemistry,Purdue University,West Lafayette,Indiana 47907,USA)

    Under weak base conditions,diruthenium(Ⅲ) tetrakis-N,N′-dimethylbenzamidinate (DMBA)nitrate Ru2(DMBA)4(NO3)2was reacted with arylethyne ligands,where aryl=NAPme(N-methyl-1,8-naphthalimide),NAPiso(N-isopropyl-1,8-naphthalimide),Naphth (naphthalene)and Ant (anthracene),to afford four new compounds:trans-Ru2(DMBA)4(C2Ar)2(Ar=NAPme,1;NAPiso,2;Naphth,3;Ant,4).Molecular structures of new compounds were determined using single crystal X-ray diffraction,and the Ru-Ru bond lengths (0.245 0~0.249 1 nm)are consistent with the existence of a Ru-Ru single bond.These compounds are diamagnetic and were further characterized with1H NMR and UV-Vis-NIR spectroscopic techniques.Cyclic voltammograms of compounds 1~4 consist of two reversible one-electron processes,an oxidation and a reduction,and their potentials depend on the nature of Ar.CCDC 1555598,1;1555599,2;1555609,3;1555611,4.

    diruthenium;alkynyl;naphthalimide;naphthalene;anthracene

    O614.82+1

    A

    1001-4861(2017)11-2103-07

    10.11862/CJIC.2017.238

    2017-06-14。收修改稿日期:2017-08-23。

    美國國家科學(xué)基金會(No.CHE 1362214,CHE 1625543)資助項目。

    *通信聯(lián)系人。E-mail:tren@purdue.edu

    猜你喜歡
    異丙基酰亞胺雙核
    全球金融“F20”在此召開!橫瀝進(jìn)入“雙核”時代
    精制2, 6-二異丙基萘的方法
    能源化工(2021年3期)2021-12-31 11:59:23
    改性雙馬來酰亞胺樹脂預(yù)浸料性能研究
    雙馬來酰亞胺對丙烯酸酯結(jié)構(gòu)膠的改性研究
    中國塑料(2017年2期)2017-05-17 06:13:21
    1種制備六氟異丙基甲醚的方法
    新型夾心雙核配和物[Zn2(ABTC)(phen)2(H2O)6·2H2O]的合成及其熒光性能
    EG/DMMP阻燃聚氨酯-酰亞胺泡沫塑料的研究
    中國塑料(2015年6期)2015-11-13 03:02:49
    聚N-異丙基丙烯酰胺/黏土納米復(fù)合自修復(fù)水凝膠的制備及性能
    中國塑料(2015年12期)2015-10-16 00:57:12
    聚琥珀酰亞胺的熱力學(xué)性質(zhì)研究
    三螺旋N-N橋連的雙核Co(Ⅲ)配合物的合成、結(jié)構(gòu)和性質(zhì)
    国产精品av视频在线免费观看| 婷婷精品国产亚洲av| 国产黄片美女视频| 国产大屁股一区二区在线视频| 亚洲第一电影网av| 给我免费播放毛片高清在线观看| 精品久久国产蜜桃| 久久精品综合一区二区三区| 又紧又爽又黄一区二区| 国产精品亚洲美女久久久| av女优亚洲男人天堂| 亚洲熟妇熟女久久| 91午夜精品亚洲一区二区三区 | a在线观看视频网站| 精品免费久久久久久久清纯| 欧美精品国产亚洲| 成人国产麻豆网| 国产真实伦视频高清在线观看 | 午夜免费激情av| 国产成年人精品一区二区| 国产精品福利在线免费观看| 国内精品一区二区在线观看| 99久国产av精品| 欧洲精品卡2卡3卡4卡5卡区| 久久精品国产亚洲网站| 99精品久久久久人妻精品| 一本久久中文字幕| 97热精品久久久久久| 午夜亚洲福利在线播放| 亚洲国产精品成人综合色| 亚洲狠狠婷婷综合久久图片| 免费大片18禁| 欧美日韩中文字幕国产精品一区二区三区| 日韩欧美一区二区三区在线观看| 久久精品久久久久久噜噜老黄 | 亚洲无线观看免费| 国产在线精品亚洲第一网站| 日本在线视频免费播放| 亚洲人成网站在线播| 国产真实乱freesex| 久久99热6这里只有精品| 真人一进一出gif抽搐免费| 美女xxoo啪啪120秒动态图| 亚洲精品国产成人久久av| 日本a在线网址| 男女视频在线观看网站免费| 国产黄色小视频在线观看| 欧美zozozo另类| 麻豆国产97在线/欧美| 一夜夜www| 嫩草影院精品99| 在线观看一区二区三区| 精品久久久久久久久亚洲 | 亚洲av日韩精品久久久久久密| 美女大奶头视频| 国产高清激情床上av| 免费av毛片视频| 久久香蕉精品热| 日韩欧美国产一区二区入口| 不卡视频在线观看欧美| 人妻制服诱惑在线中文字幕| 欧美日韩黄片免| 在线看三级毛片| 如何舔出高潮| 久久久色成人| 婷婷丁香在线五月| 午夜精品在线福利| 麻豆精品久久久久久蜜桃| 日本黄色片子视频| 国产精品一区二区免费欧美| 乱码一卡2卡4卡精品| 久久草成人影院| 亚洲成a人片在线一区二区| 成人二区视频| 欧洲精品卡2卡3卡4卡5卡区| 精品欧美国产一区二区三| 成人av在线播放网站| 欧美激情在线99| 嫩草影院入口| 中文字幕熟女人妻在线| 精品久久久久久久末码| 男女视频在线观看网站免费| 久久久色成人| 天堂√8在线中文| 国产免费av片在线观看野外av| 久久婷婷人人爽人人干人人爱| 久久久久久国产a免费观看| АⅤ资源中文在线天堂| 欧美一区二区国产精品久久精品| 男女下面进入的视频免费午夜| 亚洲欧美日韩无卡精品| 小说图片视频综合网站| 小蜜桃在线观看免费完整版高清| 少妇高潮的动态图| 91在线观看av| 亚洲国产精品久久男人天堂| 免费人成在线观看视频色| 国产色婷婷99| 中文字幕av在线有码专区| 国产毛片a区久久久久| 午夜视频国产福利| 国产高清不卡午夜福利| 国产精品乱码一区二三区的特点| 日韩中文字幕欧美一区二区| 免费在线观看日本一区| 窝窝影院91人妻| .国产精品久久| 在线观看免费视频日本深夜| 中文字幕av成人在线电影| 一区二区三区高清视频在线| 白带黄色成豆腐渣| 白带黄色成豆腐渣| 亚洲最大成人中文| 小说图片视频综合网站| 日韩精品青青久久久久久| 国产精品综合久久久久久久免费| 国产高清激情床上av| 哪里可以看免费的av片| 国产国拍精品亚洲av在线观看| 嫩草影院入口| 久久久色成人| 内地一区二区视频在线| 男人和女人高潮做爰伦理| 色尼玛亚洲综合影院| 国产色爽女视频免费观看| 人人妻人人看人人澡| 小说图片视频综合网站| 两个人的视频大全免费| av在线蜜桃| 久久香蕉精品热| 黄色一级大片看看| 免费在线观看影片大全网站| www日本黄色视频网| 国产一区二区三区av在线 | 国产成年人精品一区二区| 成人特级av手机在线观看| 在线观看美女被高潮喷水网站| 一区二区三区四区激情视频 | 中文在线观看免费www的网站| 色尼玛亚洲综合影院| 亚洲性久久影院| 中文在线观看免费www的网站| 赤兔流量卡办理| 日本黄色视频三级网站网址| 波野结衣二区三区在线| 国产精品久久久久久亚洲av鲁大| 无遮挡黄片免费观看| 91久久精品电影网| 2021天堂中文幕一二区在线观| 精品久久久久久久久亚洲 | 两人在一起打扑克的视频| av在线老鸭窝| 天天一区二区日本电影三级| 国产精品人妻久久久久久| 亚洲色图av天堂| 精品国内亚洲2022精品成人| 国产高清不卡午夜福利| 91久久精品电影网| 免费不卡的大黄色大毛片视频在线观看 | 精品人妻1区二区| 亚洲内射少妇av| 成年女人永久免费观看视频| 最近中文字幕高清免费大全6 | 两个人视频免费观看高清| 非洲黑人性xxxx精品又粗又长| 欧美成人a在线观看| 69人妻影院| 少妇猛男粗大的猛烈进出视频 | 国产v大片淫在线免费观看| 成年人黄色毛片网站| 干丝袜人妻中文字幕| 观看免费一级毛片| 成年女人毛片免费观看观看9| 日日夜夜操网爽| 亚洲欧美日韩高清在线视频| av在线亚洲专区| 欧美一区二区精品小视频在线| 欧美bdsm另类| 久久久久久国产a免费观看| 18禁在线播放成人免费| 中亚洲国语对白在线视频| 亚洲欧美日韩高清专用| 国产单亲对白刺激| 日日摸夜夜添夜夜添av毛片 | 最近最新免费中文字幕在线| 欧美一区二区亚洲| 美女 人体艺术 gogo| 啦啦啦啦在线视频资源| 成人鲁丝片一二三区免费| 中国美白少妇内射xxxbb| 午夜视频国产福利| 天堂av国产一区二区熟女人妻| 国产精品久久久久久久电影| 亚洲成人久久性| 一区二区三区高清视频在线| 日韩精品有码人妻一区| 午夜福利欧美成人| 少妇高潮的动态图| av.在线天堂| 久久精品国产自在天天线| 亚洲熟妇中文字幕五十中出| 五月玫瑰六月丁香| 国产主播在线观看一区二区| 国产精品免费一区二区三区在线| 久久精品夜夜夜夜夜久久蜜豆| 99国产极品粉嫩在线观看| 亚洲av免费在线观看| 在线免费观看的www视频| 欧美性感艳星| 啪啪无遮挡十八禁网站| 亚洲精品456在线播放app | 亚洲熟妇中文字幕五十中出| 久久中文看片网| 亚洲av美国av| 亚洲国产精品成人综合色| 最后的刺客免费高清国语| 久久精品国产99精品国产亚洲性色| 国内久久婷婷六月综合欲色啪| 成人欧美大片| 一级黄色大片毛片| 国产精品国产三级国产av玫瑰| 精品一区二区三区视频在线观看免费| 一级a爱片免费观看的视频| 午夜影院日韩av| 国产精品久久久久久精品电影| 国产三级中文精品| 国产主播在线观看一区二区| 最近最新免费中文字幕在线| 亚洲国产色片| 桃红色精品国产亚洲av| 成人亚洲精品av一区二区| 国产伦在线观看视频一区| 日韩欧美在线乱码| 国产精品电影一区二区三区| 成人永久免费在线观看视频| 一级a爱片免费观看的视频| 中文亚洲av片在线观看爽| 看十八女毛片水多多多| 国产一区二区三区av在线 | 乱码一卡2卡4卡精品| 国产精品不卡视频一区二区| 成人毛片a级毛片在线播放| 有码 亚洲区| 99久久无色码亚洲精品果冻| 国内精品宾馆在线| 日本一本二区三区精品| 搞女人的毛片| 国产三级中文精品| 国产国拍精品亚洲av在线观看| 久久久久久久久大av| 丰满乱子伦码专区| 最后的刺客免费高清国语| 午夜久久久久精精品| 日韩精品中文字幕看吧| 三级国产精品欧美在线观看| 亚洲一级一片aⅴ在线观看| 成年人黄色毛片网站| 啦啦啦观看免费观看视频高清| 久久香蕉精品热| 免费高清视频大片| 国模一区二区三区四区视频| 日韩大尺度精品在线看网址| h日本视频在线播放| 在线免费观看的www视频| 别揉我奶头~嗯~啊~动态视频| 午夜福利成人在线免费观看| 成人一区二区视频在线观看| 日本与韩国留学比较| 亚洲精品在线观看二区| 99九九线精品视频在线观看视频| 日本欧美国产在线视频| 国内久久婷婷六月综合欲色啪| 三级国产精品欧美在线观看| 欧美日韩综合久久久久久 | 丰满乱子伦码专区| 国产成人aa在线观看| 国产av一区在线观看免费| 在线观看免费视频日本深夜| 久久精品夜夜夜夜夜久久蜜豆| 亚洲精品色激情综合| 麻豆国产97在线/欧美| 国产免费av片在线观看野外av| 狠狠狠狠99中文字幕| 久久久国产成人免费| 精品久久久久久久久久久久久| 久久精品国产亚洲av涩爱 | 国产精品不卡视频一区二区| 18禁黄网站禁片免费观看直播| 少妇的逼好多水| 国产日本99.免费观看| 国产午夜精品论理片| 亚洲专区中文字幕在线| 日日撸夜夜添| 国产精品一区www在线观看 | 亚洲真实伦在线观看| 在线观看66精品国产| 成人高潮视频无遮挡免费网站| 久久这里只有精品中国| 久久久久久久精品吃奶| bbb黄色大片| 国产毛片a区久久久久| 黄色女人牲交| 久久久色成人| 亚洲av成人精品一区久久| 亚洲av中文av极速乱 | 99热这里只有是精品在线观看| 99久久九九国产精品国产免费| 国产精品国产三级国产av玫瑰| 搡老妇女老女人老熟妇| 久久精品国产99精品国产亚洲性色| 搞女人的毛片| 少妇人妻一区二区三区视频| 丰满人妻一区二区三区视频av| 欧美色视频一区免费| 日韩欧美国产在线观看| 国产精品一区二区三区四区免费观看 | 色视频www国产| 国产探花极品一区二区| 亚洲精品日韩av片在线观看| 久久天躁狠狠躁夜夜2o2o| 两人在一起打扑克的视频| 亚洲在线自拍视频| 日韩欧美精品v在线| 日日干狠狠操夜夜爽| av女优亚洲男人天堂| 伦精品一区二区三区| ponron亚洲| 88av欧美| 嫁个100分男人电影在线观看| 国产 一区 欧美 日韩| 国产伦一二天堂av在线观看| 午夜福利在线观看免费完整高清在 | 日日撸夜夜添| 亚洲欧美激情综合另类| 韩国av一区二区三区四区| 91久久精品电影网| 色综合站精品国产| 亚洲欧美精品综合久久99| 国产激情偷乱视频一区二区| 亚洲欧美日韩无卡精品| 禁无遮挡网站| 国产欧美日韩一区二区精品| 日日夜夜操网爽| av中文乱码字幕在线| 国产高清有码在线观看视频| 成熟少妇高潮喷水视频| 1000部很黄的大片| 一夜夜www| 精品久久久噜噜| 国产精品福利在线免费观看| 淫秽高清视频在线观看| 高清在线国产一区| 久久精品人妻少妇| 欧美黑人欧美精品刺激| 婷婷丁香在线五月| 日本黄大片高清| 成人午夜高清在线视频| 成人精品一区二区免费| 99视频精品全部免费 在线| 超碰av人人做人人爽久久| 九色国产91popny在线| 亚洲专区国产一区二区| 国产精品自产拍在线观看55亚洲| 尤物成人国产欧美一区二区三区| 久久精品人妻少妇| 高清毛片免费观看视频网站| 色综合婷婷激情| 亚洲成人精品中文字幕电影| 日韩高清综合在线| 精品久久久久久久久久久久久| 国产男靠女视频免费网站| 高清毛片免费观看视频网站| 国产精品99久久久久久久久| 97碰自拍视频| 久久天躁狠狠躁夜夜2o2o| 搡老熟女国产l中国老女人| 成人av一区二区三区在线看| 99久久无色码亚洲精品果冻| 国产欧美日韩精品一区二区| 国产一区二区在线观看日韩| bbb黄色大片| 亚洲第一区二区三区不卡| а√天堂www在线а√下载| 国产久久久一区二区三区| 国产精品久久久久久亚洲av鲁大| 麻豆国产97在线/欧美| 国产久久久一区二区三区| 亚洲国产高清在线一区二区三| 午夜亚洲福利在线播放| 亚洲在线观看片| 国产 一区精品| 三级毛片av免费| 日韩大尺度精品在线看网址| 22中文网久久字幕| 色精品久久人妻99蜜桃| 亚洲无线观看免费| 亚洲美女视频黄频| videossex国产| 搡老熟女国产l中国老女人| 国产精品一及| 中出人妻视频一区二区| 国产高潮美女av| 免费高清视频大片| 亚洲不卡免费看| 免费看光身美女| 国产精品精品国产色婷婷| 又爽又黄a免费视频| 国产熟女欧美一区二区| 制服丝袜大香蕉在线| a级一级毛片免费在线观看| 亚洲精品在线观看二区| 超碰av人人做人人爽久久| 男人和女人高潮做爰伦理| 少妇高潮的动态图| 亚洲精品色激情综合| 久久久久性生活片| 两个人的视频大全免费| 嫩草影院入口| 内地一区二区视频在线| 欧美日本亚洲视频在线播放| 99久久无色码亚洲精品果冻| 搡老熟女国产l中国老女人| 日日撸夜夜添| 一卡2卡三卡四卡精品乱码亚洲| 国产在线精品亚洲第一网站| 久久精品久久久久久噜噜老黄 | 99riav亚洲国产免费| 99热6这里只有精品| 1000部很黄的大片| 中国美女看黄片| 国产在线精品亚洲第一网站| av在线蜜桃| 国产精品自产拍在线观看55亚洲| 亚洲最大成人手机在线| 三级男女做爰猛烈吃奶摸视频| 香蕉av资源在线| 国产精品久久电影中文字幕| 国产精品福利在线免费观看| 亚洲美女黄片视频| 亚洲人与动物交配视频| 亚洲国产精品久久男人天堂| 久久精品久久久久久噜噜老黄 | 免费看美女性在线毛片视频| 中文字幕av在线有码专区| 欧美精品国产亚洲| 国产黄色小视频在线观看| 搡老熟女国产l中国老女人| 一个人免费在线观看电影| 精品人妻熟女av久视频| 在线天堂最新版资源| 18禁在线播放成人免费| 久久久久久久久久久丰满 | 国产主播在线观看一区二区| 午夜激情欧美在线| 国产一级毛片七仙女欲春2| 偷拍熟女少妇极品色| 麻豆av噜噜一区二区三区| 亚洲欧美日韩无卡精品| 久久久色成人| 亚洲天堂国产精品一区在线| 亚洲欧美日韩无卡精品| 成人性生交大片免费视频hd| 国产v大片淫在线免费观看| 午夜影院日韩av| 欧美黑人欧美精品刺激| 精品午夜福利在线看| 国产 一区 欧美 日韩| 亚洲第一区二区三区不卡| 午夜福利在线观看吧| 又黄又爽又免费观看的视频| 免费无遮挡裸体视频| 免费高清视频大片| 国产精品一区二区免费欧美| 赤兔流量卡办理| 成人特级av手机在线观看| 亚洲美女搞黄在线观看 | 99久久九九国产精品国产免费| 男人舔女人下体高潮全视频| 亚洲一区高清亚洲精品| av在线蜜桃| 国内毛片毛片毛片毛片毛片| 国产午夜精品论理片| 国产精品一区二区性色av| 国产亚洲av嫩草精品影院| 欧美日韩综合久久久久久 | 一级黄片播放器| 老熟妇仑乱视频hdxx| a在线观看视频网站| 一本一本综合久久| 日本-黄色视频高清免费观看| 女生性感内裤真人,穿戴方法视频| 精品久久久噜噜| 亚洲av成人av| 99热这里只有是精品50| 国产乱人视频| 国产美女午夜福利| 精品福利观看| 亚洲精品日韩av片在线观看| 亚洲精品456在线播放app | 天堂动漫精品| 精品久久久噜噜| 亚洲熟妇中文字幕五十中出| 别揉我奶头 嗯啊视频| 99久久精品热视频| 欧美3d第一页| 亚洲电影在线观看av| 最后的刺客免费高清国语| 久久香蕉精品热| 国内毛片毛片毛片毛片毛片| 特级一级黄色大片| 欧美性猛交╳xxx乱大交人| 欧美+日韩+精品| 精品免费久久久久久久清纯| 91在线观看av| 俄罗斯特黄特色一大片| 尾随美女入室| 日韩强制内射视频| 国产日本99.免费观看| 亚洲国产精品sss在线观看| 国产成人av教育| 国产精品久久久久久亚洲av鲁大| 桃红色精品国产亚洲av| 一区二区三区激情视频| 国产亚洲精品久久久com| 美女被艹到高潮喷水动态| 久久久久久国产a免费观看| 尤物成人国产欧美一区二区三区| 久久国产乱子免费精品| 免费在线观看成人毛片| 久久国产乱子免费精品| 韩国av在线不卡| 欧美日本亚洲视频在线播放| 观看美女的网站| 成人国产综合亚洲| 亚洲av一区综合| 黄色一级大片看看| 欧美xxxx黑人xx丫x性爽| 又黄又爽又免费观看的视频| 国产一区二区三区av在线 | 波多野结衣高清作品| 亚洲男人的天堂狠狠| 免费av毛片视频| 精品99又大又爽又粗少妇毛片 | 亚洲精品影视一区二区三区av| 欧美日韩综合久久久久久 | 亚洲七黄色美女视频| 免费观看精品视频网站| 国产不卡一卡二| 高清在线国产一区| 天堂动漫精品| 亚洲成a人片在线一区二区| 国产 一区精品| 欧美另类亚洲清纯唯美| 亚洲欧美日韩东京热| 色播亚洲综合网| 大又大粗又爽又黄少妇毛片口| 亚洲精品国产成人久久av| 免费人成在线观看视频色| 天堂√8在线中文| 又黄又爽又刺激的免费视频.| 国产成人福利小说| 国产精品人妻久久久久久| 超碰av人人做人人爽久久| 老师上课跳d突然被开到最大视频| 嫩草影视91久久| 国产欧美日韩一区二区精品| 久久精品人妻少妇| 亚洲无线在线观看| 亚洲va日本ⅴa欧美va伊人久久| 嫩草影院入口| 伊人久久精品亚洲午夜| 亚洲va在线va天堂va国产| 老熟妇乱子伦视频在线观看| 欧美成人a在线观看| 999久久久精品免费观看国产| 成人无遮挡网站| 女同久久另类99精品国产91| 欧美成人性av电影在线观看| 又紧又爽又黄一区二区| 欧美色视频一区免费| 国产爱豆传媒在线观看| 精品国产三级普通话版| 国产av一区在线观看免费| eeuss影院久久| 丝袜美腿在线中文| 久久香蕉精品热| 51国产日韩欧美| 国语自产精品视频在线第100页| 给我免费播放毛片高清在线观看| 久久精品人妻少妇| 国产单亲对白刺激| 日日摸夜夜添夜夜添小说| 最近视频中文字幕2019在线8| 国产色爽女视频免费观看| 看十八女毛片水多多多| 成年人黄色毛片网站| 天天一区二区日本电影三级| 午夜免费激情av| 一级黄色大片毛片| 熟女人妻精品中文字幕| 国产探花极品一区二区| 女人十人毛片免费观看3o分钟| 国产精品1区2区在线观看.| 男人和女人高潮做爰伦理| 午夜日韩欧美国产| 丝袜美腿在线中文| 国产精品国产高清国产av| 狠狠狠狠99中文字幕| 日日摸夜夜添夜夜添小说| 免费观看人在逋| 国产精品永久免费网站| 色哟哟·www| 久久草成人影院| 一a级毛片在线观看| 免费观看精品视频网站|