一种环金属铱、铂双核配合物的合成及光电性能

设计合成了一种双核环金属铱,铂配合物二[N,N-2-(2,4-二氟苯基吡啶)C3,N1](吡啶甲酸)合铱(Ⅲ)-C₆-[苯基吡啶-C3,N1](吡啶甲酸)合铂(Ⅱ)(FIrPPyPt)。 通过核磁共振仪、元素分析仪、紫外-可见吸收光谱仪和光致发光光谱仪对其结构和性能进行了表征。 结果表明,配合物FIrPPyPt的紫外-可见吸收位于250~450 nm之间,荧光发射峰位于465和493 nm。 将配合物FIrPPyPt以质量分数1%~8%掺杂到主体材料聚乙烯基咔唑(PVK)+2-(联苯-4-芳基)-5-(4-叔丁基苯)-1,3,4-噁二唑(PBD)(30%)中制作了电致发光器件,在不同电压下电致发光光谱中,显现出铱配合物和铂配合物的特征峰,波峰位于400、500和530 nm蓝绿光区发射区。 该双核配合物用于单掺杂有机白光电致发光器件具有制作简单、色稳定性和重复性好等特点,为单掺杂白光发光器件提供了一种好的思路。     

N,N-二(4'-对苯基-2,2'∶6',2″-三联吡啶)-4,13-二氮杂-18-冠-6醚的合成及其光学性能

以Pd(OAc)2/PBut3为催化剂,4'-(对溴苯基)-2,2'∶6',2″-三联吡啶与二氮杂-18-冠-6经取代反应合成了新化合物N,N-二(4'-对苯基-2,2'∶6',2″-三联吡啶)-4,13-二氮杂-18-冠-6-醚(4),收率58.8%,其结构经1H NMR,13C NMR和FT-IR表征。利用紫外光谱和荧光发射光谱研究了4的光学性能,结果表明:4在甲醇中的最大紫外吸收位于358 nm;在350 nm激发波长激发下,4在二氯甲烷中的最大荧光发射峰位于458 nm。     

4-硝基-4'-(N,N-二苯基氨基)-1,2-二苯乙烯的固相合成及其光学性质

采用固相研磨法,4-(N,N-二苯基氨基)苯甲醛和溴化(4-硝基苯甲基)三苯基膦经Wittig反应合成了一种光功能材料中间体——4-硝基-4'-(N,N-二苯基氨基)-1,2-二苯乙烯(1),收率45.5%,其结构经1H NMR,13C NMR,IR和MS确证。UV-Vis和FL研究结果表明:1在295 nm和400 nm~420 nm处有较强紫外吸收;溶剂极性对1的FL谱图有明显影响,随着溶剂极性增大,出现明显猝灭现象,并发生红移。     

含取代噻吩环吡啶酰胺分子的微波合成与光谱表征

利用无溶剂微波合成法制备了两种新颖的取代噻吩基修饰吡啶酰胺分子吡啶-2,6-二[N-(2'-噻吩基甲基)甲酰胺](L1)和吡啶-2,6-二[N-(2'-噻吩基乙基)甲酰胺](L2),其合成过程无需溶剂,反应速度快,操作简单,节能环保。通过元素分析、1H-NMR、13C-NMR、IR及UV等表征手段对目标化合物L1和L2的分子结构进行了确认,对化合物的核磁谱线、红外特征吸收峰及紫外最大吸收峰进行了归属分析,丰富了吡啶酰胺类化合物的光谱数据。     

双枝[1,3,4]-噁二唑衍生物的合成与荧光性质

通过Wittig反应和Heck反应合成了三个双枝噁二唑衍生物: N-{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}二苯胺(BBOD-2), N,N-双{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}苯胺(BBOD-3), N,N,N-三{4-{2-{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}苯基}胺(BBOD-4). 化合物结构经过红外光谱、核磁共振谱、质谱和熔点确证, 测定了它们在不同溶剂中的紫外光谱和单光子荧光光谱. BBOD-1, BBOD-2, BBOD-3, BBOD-4在二氯甲烷中的最大吸收峰分别位于295, 390, 398和408 nm; 最大发射峰分别为360, 486, 483和487 nm. 讨论了Stokes位移与溶剂极性的关系.     

Y型三苯胺生色分子的二阶极化率

通过Knoevenagel反应合成了3个Y型三苯胺生色分子N,N-二{4-[2-(2-苯并噻唑基)乙烯基]苯基}苯胺(BBtVPA)、N,N-二{4-[1-(2-苯并噻唑基)-1,3-丁二烯-4-基]苯基}苯胺(BBtBPA)和N,N-二{4-[1-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢-4-呋喃基)-1,3-丁二烯-4-基]苯基}苯胺(BCfBPA), 以及4个一维偶极分子4-[2-(2-苯丙噻唑基)乙烯基]-N,N-二苯基苯胺(BtVPA)、1-(2-苯并噻唑基)-4-[4-(N,N-二苯基)氨基]苯基-1,3-丁二烯(BtAPB)、1-[(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢)-4-呋喃基]-4-[4-(N,N-二苯基氨基)]苯基-1,3-丁二烯(CfAPB)和4-[2-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢呋喃-4-基)乙烯基]-N,N-二苯基苯胺(CfVPA). 测定了生色分子的紫外吸收和荧光性质, 在二氯甲烷中, Y型分子BBtVPA, BBtBPA和BCfBPA的最大吸收波长分别为425, 443和613 nm, 比偶极分子红移了约30 nm, Y型分子BBtVPA和BBtBPA的最大荧光发射峰分别位于516和558 nm, 比偶极分子稍有红移. 根据双能级模型理论, 用溶致变色法测定了生色分子的二阶非线性极化率(β), Y型分子BBtVPA, BBtBPA和BCfBPA的β0分别为40×10-30, 64×10-30和238×10-30 esu, 比相应的偶极分子分别提高了0.9~2.8倍. 结果表明, 提高吸电子基团强度, 增大共轭体系有助于获得更大的β值.     

1,1-二苯基(或4,4'-二溴二苯基)-3-(3-三乙氧基硅基)丙基脲的合成

以三乙胺为缚酸剂,二苯胺和4,4'-二溴二苯胺分别与三光气反应制得N,N-二苯基氨基甲酰氯(2a)和N,N-(4,4'-二溴二苯基)氨基甲酰氯(2b);2a和2b分别与3-氨丙基三乙氧基硅烷反应合成了两个新型的含非对称取代脲的功能性有机硅氧烷——1,1-二苯基-3-(3-三乙氧基硅基)丙基脲和1,1-(4,4'-二溴二苯基)-3-(3-三乙氧基硅基)丙基脲,其结构经1H NMR,13C NMR和IR表征。     

基于稀土配合物的有机光盲型紫外探测器

使用二苯甲酰甲烷-二苯菲罗啉-铕(Eu(DBM)3BPhen)作为电子给体和[6,6]-苯基-C61-丁酸酸甲酯([60]PCBM)作为电子受体制备了一种新型的有机光盲型紫外探测器.在光强为2.1 mW cm-2且波长为360 nm的紫外光照射下,获得了26 mA W-1的响应度和9.1%的外量子效率,这是由于Eu(DBM)3BPhen的强紫外光吸收能力和长达300μs的激子寿命使得给受体界面处具有较高的激子解离率.在把[60]PCBM掺入Eu(DBM)3BPhen后,观察到了明显的光致发光猝灭和光电导现象.由于材料较低的载流子迁移率和受陷激子的缓慢释放,在紫外光照射关闭后,观察到了较强的持续光电导现象.     

三苯胺-吡啶衍生物的三光子吸收及光限幅特性

合成了3个三苯胺-吡啶衍生物4-乙烯基吡啶-4'-(N,N-二苯胺基)苯(PPAB)、三[4-(4-吡啶乙烯基)苯]胺(TPPA)和4-(对-甲基-乙烯基吡啶碘盐)-4'-(N,N-二苯胺基)苯(PBPI),研究了它们的单光子荧光和三光子荧光性质.在1310nm飞秒激光激发下,化合物PPAB,PBPI and TPPA在二氯甲烷溶液中发出很强的三光子上转换荧光,荧光峰分别位于648,625,696nm.用飞秒Ti:Sapphire激光器非线性透过率法测得3个化合物在1310nm三光子吸收截面分别为1.91×10-79,3.46×10-79,3.64×10-79cm6·s2,它们具有很强的三光子吸收和光限幅效应.     

聚合方法对聚苯胺性能的影响北大核心CSCD

分别通过苯胺的化学氧化以及N,N-二氯对苯醌二亚胺与对二溴苯格氏试剂在Ni(Ⅱ)配合物催化下共聚等两种方法合成了聚苯胺。对两种方法所获得的聚合物通过红外光谱(FT-IR)、紫外可见吸收光谱(UVVis)、循环伏安(CV)、充放电等对聚合物进行了表征和性能测试。结果表明,化学氧化法合成聚苯胺的紫外-可见吸收光谱中,在600nm处出现最大吸收峰,而金属配合物催化法合成的聚合物最大吸收峰出现在443nm。两种聚合物都具有可逆的氧化-还原性能,其氧化峰分别出现在0.26eV和0.49eV处。     

Molecular design and theoretical investigation into one-and two-photon absorption properties of two series of cyclometalated platinum(Ⅱ) complexes

We have theoretically investigated two series of cyclometalated Pt(Ⅱ) complexes,a series [Pt(C,N,N) Cl] and b series [Pt(C,N,Npyrazolyl) Cl].The geometrical and electronic structures are calculated at the ECP60MWB//6-31G*(H,C,Cl,N,S) basis set level using DFT method;one-photon absorption(OPA) properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption(TPA) properties are obtained with the ZINDO/SOS method.The resonance integrals parameters(βsp and βd) for Pt are adjusted to -1 and -28.5 eV,respectively,to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results.The calculated results indicate the molecule 2b([Pt(Cnaphthyl,N,Npyrazolyl) Cl]) has the biggest potential as outstanding TPA materials because(i) the TPA properties of b series are more outstanding in IR wavelength range,the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination(e.g.,dimerization) and chemical interactions;(ii) when C is Cnaphthyl in the C,N,N ligand of cyclometalated Pt(Ⅱ) complexes,the molecules have the best conjugation effect and the best TPA properties.     

Blue luminescent 2-(2'-pyridyl)benzimidazole derivative ligands and their orange luminescent mononuclear and polynuclear organoplatinum(II) complexes

Five new 2-(2'-pyridyl)benzimidazole derivative ligands, 1,4-bis[2-(2'-pyridyl)benzimidazolyl]benzene (1,4-bmb), 4,4'-bis[2-(2'-pyridyl)benzimidazolyl]biphenyl (bmbp), 1-bromo-4-[2-(2'-pyridyl)benzimidazolyl]benzene (Brmb), 1,3-bis[2-(2'-pyridyl)benzimidazolyl]benzene (1,3-bmb), and 1,3,5-tris[2-(2'-pyridyl)benzimidazolyl]benzene (tmb), have been synthesized by Ullmann condensation methods. The corresponding mononuclear and polynuclear PtII complexes, Pt2(1,4-bmb)Ph4 (1), Pt2(bmbp)Ph4 (2), Pt(Brmb)Ph2 (3), Pt2(1,3-bmb)Ph4 (4), and Pt3(tmb)Ph6 (5), have been obtained by the reaction of the appropriate ligand with [PtPh2(SMe2)]n. The structures of the free ligands 1,4-bmb, bmbp, and tmb, as well as the complexes 1-3, were determined by single-crystal X-ray diffraction. All ligands display fluorescent emissions in the purple/blue region of the spectrum at ambient temperature and phosphorescent emissions in the blue/green region at 77 K, which are attributable to ligand-centered pi --> pi* transition. No ligand-based emission was observed for the PtII complexes 1-5. All PtII complexes display orange/red emissions at 77 K in a frozen solution or in the solid state, attributable to metal-to-ligand charge transfers (MLCT). Variable-temperature 1H NMR experiments establish that complexes 1, 4, and 5 exist in isomeric forms in solution at ambient temperature due to the hindered rotation of the square PtC2N2 planes in the complexes.     

Ortho-platinated metallomesogens based on rod mesogenic unit of 2-phenylpyridine derivatives: synthesis,high linearly polarised and phase-state-dependent luminescence

Three series of cyclometalated platinum (II) complexes [(cbC_nppyC₁₆) Pt(acac) (a_n), (cbC_nppyC₁₆)Pt(pic) (b_n) and (cbC_nppyC₁₆)Pt(picd) (c_n)] were obtained, where cbC_nppyC₁₆ (2-(4-hexadecyloxyphenyl)-5-[(1,1?-biphenyl)-4-carbonitrile-4?-alkoxy-methoxyl]pyridine) is as cyclometalated ligand, and Hacac (acetylacetone), Hpic (picolinic acid) and Hpicd (5-[(1,1?-biphenyl)-4-carbonitrile-4?-dodecyloxy]oxy-2-car boxylpyridine) are auxiliary, respectively. The liquid crystalline behaviour, polarised emission, photophysical and phase-state-dependent luminescence properties for all platinum (II) complexes were investigated systematically. Cyclometalated platinum (II) complexes b_n show smectic phase structure; however, a_n and c_n show nematic phase. The platinum (II) complexes exhibit different photoluminescence (PL) behaviour in solution, crystal phase, liquid crystal phase and amorphous thin films. Moreover, these metallomesogens show strongly polarised photouminescence in liquid crystalline phases. Especially, the PL dichroic ratio is up to 24.6 in nenatic phase.     

The synthesis and photophysical studies of cyclometalated Pt(II) complexes with C,N,N-ligands containing imidazolyl donors

Two new C,N,N-type ligands (HL(2) and HL(3)), containing a C(phenyl), a N(pyridyl), and a N(imidazolyl) donor, and their cycloplatinated complexes, [Pt(L(2))Cl] (1), [Pt(L(3))Cl] (2), [Pt(L(2))(PPh(3))](+) (3) and [Pt(L(3))(PPh(3))](+) (4), have been successfully synthesized and characterized. Spectroscopic and (3)MLCT luminescent properties of these Pt(II) cyclometalated complexes were found to be pH dependent. This was attributed to the protonation/deprotonation of the acidic 1-imidazolyl-NH moieties on the ligands. All the cycloplatinated complexes (both protonated and deprotonated forms) possessed two-photon excitability with two-photon absorption cross-sections ranging from 6.0 to 30.0 GM (protonated forms) and from 16.2 to 24.9 GM (deprotonated forms).     

Luminescent organoplatinum(II) complexes with functionalized cyclometalated C^N^C ligands: structures, photophysical properties, and material applications

A series of [(R'-C^N^C-R')Pt(L)] complexes with doubly deprotonated cyclometalated R'-C^N^C-R' ligands (R'-C^N^C-R'=2,6-diphenylpyridine derivatives) functionalized with carbazole, fluorene, or thiophene unit(s) have been synthesized and their photophysical properties studied. The X-ray crystal structures reveal extensive intermolecular π···π and C-H···π interactions between the cyclometalated C^N^C ligands. Compared to previously reported cyclometalated platinum(II) complexes [(C^N^C)Pt(L)], which are non-emissive in solution at room temperature, the carbazole-, fluorene- and thiophene-functionalized [(R'-C^N^C-R')Pt(L)] (L=DMSO 1-9, C≡N-Ar, 1a-9a) complexes are emissive in solution at room temperature with λ(max) at 564-619 nm and Φ=0.02-0.26. The emissions of the [(R'-C^N^C-R')Pt(L)] complexes are attributed to electronic excited states with mixed (3)MLCT and (3)IL character. The carbazole/fluorene/thiophene unit(s) allow the tuning of the electronic properties of the [(R'-C^N^C-R')Pt] moiety, with the emission maxima in a range of 564-619 nm. These are the first examples of organoplatinum(II) complexes bearing doubly deprotonated cyclometalated C^N^C ligands that are emissive in solution at room temperature. In non-degassed DMSO, the emission intensities of 6a-9a are enhanced upon exposure to ambient light. This phenomenon is caused by reacting photogenerated (1)O(2) with a DMSO molecule to form dimethyl sulfone, leading to the removal of dissolved oxygen in solution. Self-assembled nanowires and nanorods are obtained from precipitation of 3a in THF/H(2)O and 8a in DMSO/Et(2)O, respectively. The [(R'-C^N^C-R')Pt(L)] complexes are soluble in common organic solvents with a high thermal stability (>300 °C), rendering them as phosphorescent dopants for organic light-emitting diode (OLEDs) applications. Red OLEDs with CIE coordinates of (0.65±0.01, 0.35±0.01) were fabricated from 7a or 8a. A maximum external efficiency (η(Ext)) of 12.6% was obtained for the device using 8a as emitter.     

含氮配体Co、Fe配合物的合成、结构及性质

报导了四个单核Co（Ⅱ）和Fe（Ⅱ）的配合物[Co（L1）2]（ClO4)2·（CH3CN）（1）,[Fe（L1）2]（ClO4）2·（H2O）（2）,[Co（L2）]（ClO4）2（3）,以及[Fe（L2）]（ClO4）2·2H2O（4）,（其中L1＝4’-苯基-2,2’：6’,2”-三联吡啶,L2＝N,N,N-三-（2-（2-吡啶甲叉氨基）乙基）胺）的合成和性质,以及配合物1、3的晶体结构．配合物1和3的晶体都属于单斜晶系．它们的晶胞参数分别为：1a＝1．0855（4）nm,b＝1．6201（5）nm,c=2.5236（5）nm,β＝92．63（2）°,V＝4．433（1）nm3;3a=2.8351（8）nm,b＝1．0670（3）nm,c＝1．9255（5）m,β＝101．03（4）°,V＝5717（2）nm3．2和4的氧化还原电位分别为E＝0．78V和0．63V‘它们的d-d跃迁吸收最大值分别位于565和521nm处．     

Metallomesogens based on platinum(II) complexes: synthesis, luminescence and polarized emission

Two series of heteroleptic cyclometalated platinum(II) complexes [(C(n)Oppy)Pt(acac) and (C(n)OFppy)Pt(acac)] have been prepared. Their liquid-crystal and optophysical properties were studied, in which C(n)Oppy is 2-(4-alkoxyphenyl)-5-(alkoxymethyl)pyridine and C(n)OFppy is 2-(3-fluoro-4-alkoxyphenyl)-5-(alkoxymethyl)pyridine. Only the heteroleptic cyclometalated platinum(II) complexes (n = 12 and 16) exhibited enantiotropic mesophase transitions with smectic (S(m)) structure. Intense polarized luminescence with a maximum peak at 532 nm and a polarization ratio as high as 10.5 were obtained in an aligned polyimide film under opto-excitation at room temperature. This research work provides a simple approach to realize high-efficiency polarized emission by heteroleptic cyclometalated platinum(II) complexes.     

5-(4′-烷氧基苯基)-8-羟基喹啉锌的合成及其偏振发光性能

本文通过在8-羟基喹啉的5位上引入含不同碳链长度的对烷氧基苯基,合成了一类5-(4′-烷氧基苯基)-8-羟基喹啉锌配合物(C6OphQ)2Zn、(C8OphQ)2Zn和(C12OphQ)2Zn。通过DSC和偏振显微镜等热力学仪器考察了它们的液晶性,发现长链的5-对烷氧基-苯基-8-羟基喹啉锌均具有液晶性。将它们在聚酰亚胺取向薄膜上进行排列,应用装备有偏振器的紫外分光光度计和荧光分光光度仪测定了薄膜偏振光性质。实验发现,这些具有液晶性质的发光配合物在聚酰亚胺取向薄膜上能够产生有序排列,表现出一定的吸收和发射二色比。其中配合物(C8OphQ)2Zn在332 nm处的最大吸收二色比是2.0,在500 nm处的发射二色比为2.4。     

Electroluminescent properties of three ternary europium complexes with different phenanthroline derivatives

In the past decade a number of lanthanide com-plexes have been designed and synthesized for organic electroluminescent (EL) devices owing to their ex-tremely sharp emission bands and potentially high internal quantum efficiency[113]. This characteristic made the lanthanide complexes one kind of promising candidates for full color flat-panel displays which re-quire pure red, green and blue emissions. So far, how-ever, the devices based on lanthanide complexes as emitters have not demonstrated v…