5,9,14,18,23,27,32,36-八烷氧基2,3-萘酞菁镍(Ⅱ)的结构与光谱性质关系的研究

测定了一组八烷氧基萘酞菁镍（Ⅱ）配合物Ni（Ⅱ）（RO）8NPC（R＝C4H9，C8H17，C12H25，NPC＝C48H16N8）在5种有机溶剂（Py、DMSO、DMF、CH2Cl2、C6H12）中的电子吸收光谱和荧光光谱，研究了这些配合物的结构与光谱的关系。结果表明该系列RO取代萘酞菁镍（Ⅱ）配合物的Q带吸收光谱比无取代的红移75nm左右，荧光光谱屯相应红移50～80nm，而溶剂对其影响不大。     

Synthesis of Oligomeric Axially Bridged Ruthenium Phthalocyanines and 2,3-Naphthalocyanines

Bridged 2,3-naphthalocyaninatoruthenium oligomers {[MacRu(L)] _n } were synthesized and characterized using solid-state methods. For comparison, soluble t-butyl substituted phthalocyaninatoruthenium oligomers were prepared and their chain length examined by ¹H NMR spectroscopy. The powder conductivities of all bridged compounds ([MacRu(L)] _n ) were measured and the dependence of the conductivities on the bridging ligands is discussed.     

非水溶剂中八丁氧基2，3－萘酞菁氯锰（Ⅲ）的电化学研究

非水溶剂中八丁氧基２,３ 萘酞菁氯锰（Ⅲ）的电化学研究①杨素苓刘尔生陈耐生黄金陵（福州大学化学系,福州３５０００２）王晓玉卜平段武彪吴谊群左霞（黑龙江大学化学系,哈尔滨１５００８０）金属萘酞菁配合物由于含有比相应的酞菁配合物更大的π 共轭体系,因而具...     

萘酞菁铅化合物的光限幅特性研究

应用调Q倍频ns/ps Nd：YAG脉冲激光,在波长为532nm,脉冲宽度为8ns,重复频率为1Hz的条件下,研究了溶于二甲基亚砜(DMSO)中的萘酞菁铅溶液的反饱和吸收和光限幅特性。实验表明,萘酞菁铅具有良好的光限幅特性,它的有效激发态吸收截面与基态吸收截面的比值约为15．21,大于萘酞菁铜。研究结果表明,萘酞菁铅的光限幅特性优于C60,激发态吸收是其主要的光限幅机理。实验结果证实了重原子效应可以通过增强系际跃迁而使三重态的反饱和吸收增强,从而提高光限幅的能力。     

Synthesis and characterization of near-infrared absorption tin octabutoxy naphthalocyanines

Synthesis and characterization of a series of tin octabutoxy naphthalocyanines are presented, which show near infrared absorptions (900–930 nm) with high extinction coefficients (ca. 1 × 10⁵ M⁻¹ cm⁻¹). The position of the Q-band is more red-shifted with the heavier halogen, which corresponds to the HOMO–LUMO gaps calculated with density functional theory (0.932, 0.911, 0.905, 0.893 eV). The interaction with SnNc(OBu)₈Br₂ and C₆₀ moves the Q-band further to the infrared region (928 nm). In ¹¹⁹Sn NMR, the upfield shift (−120 ppm) of SnNc(OBu)₈I₂ represents a relatively electron-rich environment at the tin nucleus, and the ¹¹⁹Sn-resonance (237 ppm) of SnNc(OBu)₈F₂ is different from the other halides, where ¹¹⁹Sn–¹⁹F coupling, a triplet splitting (1:2:1), was observed with 1820 Hz coupling constant. In the optimized structures obtained with BLYP, the distortion angles vary from F to I (N–Sn–N angles 178.8°, 173.1°). The tin naphthalocyanine with the heavy halide ligand becomes more concave, and the Sn–X bond is located at a longer distance out of ring. The difference of the two axial bonds varies significantly from 0.003 to 0.104 Å with the change of the axial ligands from F to I. The distorted shape is larger in the order I > Br > Cl > F with increase of the atomic size (1.33, 1.15, 0.99, 0.71 Å, respectively) and decrease of electronegativity (2.21, 2.74, 2.83, 4.10, respectively). SnNc(OMe)₈X₂ has an electric dipole moment perpendicular to the naphthalocyanine plane, and the magnitudes are, 0.81, 0.50, 0.35 and 0.01 for F, Cl, Br and I, respectively. The transition dipole moment lies in the naphthalocyanine plane along the x- or y-axis perpendicular to the permanent dipole moment in the z-axis, which indicates a π → π^∗ ligand–ligand transition. The energies of the molecular orbitals which are mainly contributed to by the naphthalocyanine ring, including the HOMO and LUMO, are slightly changed as the axial ligands change from F to I.     

一个对称萘酞菁的LB膜及其二阶非线性光学性质的研究

用水平提拉法制备了四叔丁基萘酞菁锌的LB膜。利用表面压-面积曲线、紫外-可见吸收光谱、小角X-射线衍射等表征了LB膜的结构,结果表明该化合物可以形成较高质量的具有很好层状结构的多层LB膜,在膜中分子大环平面垂直于基片平面并且以分子平面并不完全重合的H-聚集体存在。采用透射SHG方法测量了相应LB膜的二阶非线性光学性质,结果显示在实验条件下该化合物LB膜的宏观二阶非线性系数以及分子超极化率分别为X     

How pulse train parameters take effect on nonlinear dynamics of naphthalocyanines and phthalocyanines?

In this work, we study the influences of different pulse train parameters on nonlinear dynamics of naphthalocyanines and phthalocyanines. The total number of subpulses, width of each subpulse and time spacing between subpulses are discussed in detail. A two-dimensional paraxial field equation coupled with rate equations is solved numerically using the Crank--Nicholson method. We use photophysics parameters of molecules extracted from experimental work and our theoretical result shows the same optical limiting behaviours with the experiment.     

萘酞菁锌复合体系的光致电荷转移

合成了萘酞菁锌, 利用傅立叶红外光谱、元素分析和MALDI-TOF质谱等手段表征了分子结构; 循环伏安测试和吸收光谱确认了共轭体系的扩大使分子带隙下降. 根据材料加工性能的不同, 分别采用溶液法、层-层蒸镀(Layer-by-layer evaporation)法和单层分散旋涂法, 将给体分子萘酞菁锌与三种受体分子1-(3-甲氧基羧基)丙基-1-苯 基-[6,6]C61, C60和N,N’-二嘧啶基苝四羧基二酰亚胺进行了复合, 通过研究复合前后荧光变化, 确认了给体-受体两相界面处发生了由分子能级差引发的光致电荷转移, 为制备更宽光伏响应范围的太阳能电池器件提供了潜在的新途径.     

萘酞菁化合物LB膜的二阶非线性光学特性研究

研究了四种萘酞菁化合物LB膜的制备和二阶非线性光学特性 ,并对它们的二阶非线性产生机理进行了简单的讨论。不对称萘酞菁化合物的二阶非线性起源于电偶极子机制 ;对称萘酞菁化合物的二阶非线性起源于磁偶极子耦合机制。二阶非线性最大的三叔丁基氰基萘酞菁的二阶非线性极化率 χ( 2 ) 为 3 7× 10 - 8esu ,约为三叔丁基萘酞菁的 37倍     

Synthesis and nonlinear optical properties of fluorine-containing naphthalocyanines

The fluorine-containing metal naphthalocyanines [F16NcGaCl] (7) and [(F16NcGa)2O] (8), which represent the first examples of peripherally fluorine substituted naphthalocyanines, were synthesized, and the nonlinear optical transmission was studied. Peripheral substitution by fluorine atoms enhances the solubility and photostability of the naphthalocyanines. In particular, for the axially mu-oxo-bridged naphthalocyanine dimer 8, practically no aggregation was observed in organic solvents and it has proved to be an efficient optical limiter when irradiated with laser light pulses at the wavelength of 532 nm, with pulse duration of 5 ns and repetition rate of 20 Hz.