Peripherally tetra-palladated phthalocyanines

Phthalocyanines (M = Co, Zn or 2H) with four ({4-[(Z or E)-phenylazo]-1-naphthyl}oxy) substituents on the periphery have been synthesized to enlarge the absorbing range of the dyestuffs. Cyclopalladation of the azobenzene groups lead to network-type oligomeric products by formation of binuclear palladium (II) complexes and they have been further converted into monomeric species by treatment with acetylacetonate. The electronic spectra clearly indicate the absorptions resulting from phenylazo and naphthyl groups along with the Q and B bands of the phthalocyanines. The consequence of the palladation is a relatively intense broad absorption due to LMCT with maxima around 520 nm.     

A novel indicator series for measuring pKa values in acetonitrile

A series of substituted azobenzene dyes was found to span a range of 8 pK_a units in acetonitrile. The UV absorption spectra of the dyes are responsive to protonation, changing in both absorption maximum and intensity. These characteristics make the dyes useful as indicators for the measurement of pK_a values of neutral organic bases that absorb in the visible region of the spectrum.     

A theoretical study of the lowest electronic states of azobenzene: the role of torsion coordinate in the cis–trans photoisomerization

In the present paper we report the results of a multiconfigurational computational study on potential-energy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S₂(*) and S₁(n*) states. We have found that there is a singlet state, S₃ at the trans geometry, on the basis of the doubly excited configuration n²*², that has a deep minimum at about 90° of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S₂(*) and for the wavelength-dependence of azobenzene photochemistry. We have characterized the S₁(n*) state by calculating its vibrational frequencies, which are found to correspond to the recently observed transient Raman spectrum. We have also computed the potential-energy curve for the triplet T₁(n*) at the density functional theory B3LYP level, which indicates that in this state the isomerization occurs along the twisting coordinate.Acknowledgement The financial support from MIUR (project Modellistica delle proprietà spettroscopiche di sistemi molecolari complessi funds ex 60% and project Dinamiche molecolari in sistemi di interesse chimico funds ex 40%), from the University of Bologna (Funds for Selected Research Topics) is gratefully acknowledged.Contribution to the Jacopo Tomasi Honorary Issue     

末端碳链长度对偶氮苯自组装膜结构的影响

The end-group dominated molecular orientation in the azobenzene self-assembled monolayers (SAMs), CnAzoC2SH (n=1-4), on gold was evaluated for the first time by grazing incidence reflection absorption FTIR spectroscopy (RA-FTIR). All these azobenzene SAMs have highly-organized and closely-parked structures, with the molecule tilting away gradually from surface normal direction with the increase of end group alkyl length.     

偶氮苯光致异构化对紫精-曙洪络合的调控

报导了α，ω－偶氮苯，紫精双发色团化合物的合成与性质研究，结果表明偶氮苯的光致顺反异构化以可调控与之相连的紫精与曙红络合行为，其作用程度的强弱与连接两者的亚甲基链的长度有关，借助ＨＮＭＲ通过对构象进行分析解释了上述的研究结果。     

偶氮苯自组装单分子膜中长程电子转移机理

利用自组装技术在金电极表面构造了具有不同前端健长度偶氮苯功能化的单分子膜体系：Au／S（CH2）nNHCO-N＝N-OCH2CH3（n＝2，3，4，6）．研究结果表明，仍氮苯到金电极的表现电子转移速率随它们之间的距离长度的增加而呈指数性的下降趋势．基于Marcus电子隧穿理论，得到了此自组装膜体系的长程电子隧穿系数ρ＝（1．35±0．2）／CH2在和可逆电活性分子自组装膜体系及理论计算相比较的基础上，从偶氮苯分子自组装膜结构与电子转移过程的关系角度对这一结果进行了分析和说明．     

The surface catalytic mechanism: a comparative study with square-wave and staircase cyclic voltammetry

A pseudo-first-order catalytic mechanism in which both reactant and product of a redox reaction are strongly immobilized on an electrode surface is theoretically analysed under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV). A mathematical procedure is developed under diffusionless conditions. The relationships between the properties of the voltammetric response and both the kinetic parameters of the redox reaction and the parameters of the excitation signal are studied. The phenomenon of the quasi-reversible maximum is discussed. A comparative study between SWV and SCV is presented and the limitations and advantages of both techniques, from analytical and kinetic points of view, are discussed. The theoretical predictions are experimentally confirmed by the redox reaction of azobenzene in the presence of hydrogen peroxide as an oxidizing agent. Electronic Publication     

Phosphorus-Containing Dendrimers: Synthesis and Properties

Several series of phosphorus-containing dendrimers have been designed to study the variation of their properties, depending on the type, the location (surface, branches, core, and cavities), and the number of functions implied.     

Novel Azobenzene-Functionalized Polyelectrolytes of Different Substituted Head Groups 2: Control of Surface Wetting in Self-Assembled Multilayer Films

A novel set of light-responsive polyelectrolytes has been developed and studied, to control and tune surface wettability by introducing various types of substituted R head-groups of azo polyelectrolytes in self-assembled multilayer (SAMU) films. As part of a larger project to develop polymer surfaces where one can exert precise control over properties important to proteins and cells in contact, photo-reversibly, we describe here how one can tune quite reliably the contact angle of a biocompatible SAMU, containing a photo-reversible azo chromophore for eventual directed cell growth. The azo polyelectrolytes described here have different substituted R head-group pairs of shorter-ionized hydrophilic COOH and SO₃H, shorter non-ionized hydrophobic H and OC₂H₅, and larger non-ionized hydrophobic octyl C₈H₁₇ and C₈F₁₇, and were employed as polyanions to fabricate the SAMU onto silicon substrates by using the counter-charge polycation PDAC. The prepared SAMU films were primarily characterized by measurement of their contact angles with water. The surface wetting properties of the thin films were found to be dependent on the type of substituted R-groups of the azo polyelectrolytes through their degree of ionization, size, hydrophobicity/hydrophilicity, solubility, conformation, and inter-polymeric association and intra-polymeric aggregation. All these factors appeared to be inter-related, and influenced variations in hydrophobic/hydrophilic character to different extents of aggregates/non-aggregates in solution because of solvation effects of the azo polyanions, and were thus manifested when adsorbed as thin films via the SAMU deposition process. For example, one interesting observation is significantly higher contact angles of 79° for SAMU films of larger octyl R groups of PAPEA-C₈F₁₇ and PAPEA-C₈H₁₇ than for others with contact angles of 64° observed for non-polar R-groups of OC₂H₅ and H. Furthermore, lower contact angle values of 59° for SAMU films with polar R-groups of COOH and SO₃H relative to that of non-polar R-groups are in accordance with their expected order of the hydrophilicity or hydrophobicity. It is possible that the large octyl groups are more effective in shielding the ionic functional groups on the substrate surface, and contributed less to the water drop-molecule interactions with ionic groups of the PDAC and/or AA groups. In addition, higher hydrophobicity of the SAMU films may be due to the incorporation of bulky and hydrophobic groups in these polyelectrolytes, which can produce aggregates on the surfaces of the SAMU films. Through understanding and controlling the complex aggregation behavior of the different substituted R-groups of these azo polyelectrolytes, and hence their adsorption on substrates, it appears possible to finely tune the surface energy of these biocompatible films over a wide range, enhance the photo-switching capabilities of the SAMU films, and tailor other surface properties for the development and application of new devices in diverse areas of microfluidics, specialty coatings, sensors, and biomedical sciences.