Synthesis and Surface‐Spectroscopic Characterization of Photoisomerizable glyco‐SAMs on Au(111)

Photoisomerizable glyco‐SAMs (self‐assembled monolayers), utilizing synthetic azobenzene glycoside derivatives were fabricated. The ultimate goal of this project is to assay the influence of the 3D arrangement of sugar ligands on cell adhesion, and eventually make cell adhesion photoswitchable. However, it is a prerequisite for any biological study on the spatial conditions of carbohydrate recognition, that photoisomerization of the surface molecules can be verified. Here, we employed IRRAS and XPS to spectroscopically characterize glyco‐SAMs. In particular and unprecedented to date, we prove reversible E→Z→E isomerization of azobenzene glycoside‐terminated SAMs.     

Rational construction of self-assembly azobenzene derivative monolayers with photoswitchable surface properties

hoto-responsive azobenzene (ABZ) derivatives with different end groups (R) were employed to construct selfassembled monolayers (SAMs) on silicon substrates. The SAMs based on hydrophilic (4-(4'-aminophenylazo) benzoic acid, ABZ-COOH) show excellent reversible photoswitching performance with a large contact angle change of 35° under optimized process.     

Correlation between the molecular structure and photoresponse in aliphatic self-assembled monolayers with azobenzene tailgroups

We have compared the structural and photoisomerization properties of self-assembled monolayers (SAMs) comprising either the trans or cis isomers of azobenzene terminated dithiolane with in-chain amide unit, viz., 4-(phenyldiazenyl)phenyl-4-(1,2-dithiolane-3-yl)-butylcarboxamide ( 1). These films were prepared on Au(111) from solutions of both isomers. Structure and composition of the SAMs were studied by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The photoresponse of the films was monitored in real time by ellipsometry. SAMs fabricated from the trans isomer were found to be densely packed and highly ordered. These films did not show any discernible photoresponse upon irradiation with UV light, which, under favorable conditions, triggers the trans- cis isomerization. In contrast, films prepared from solutions containing predominantly the cis isomer were loosely packed and mostly disordered but exhibited reversible photoreactivity. The results confirm that steric effects, i.e., available free volume, play a dominant role for the photoresponse of aliphatic SAMs bearing the photoactive azobenzene group. The crystal structure of 1 ( trans isomer) exhibits a row-like aggregation of neighboring molecules by weak hydrogen bonds and can be taken as a model for the arrangement of 1 in the monolayer films. Further, in addition to the surface coordination behavior, we have also mimicked the chemisorption of the 1,2-dithiolane moiety onto the gold substrate in molecular coordination chemistry in oxidative addition reactions with the zero-valent platinum complex [Pt(PPh 3) 4].     

Azobenzene-Substituted Triptycenes: Understanding the Exciton Coupling of Molecular Switches in Close Proximity

Herein, we report a series of azobenzene-substituted triptycenes. In their design, these switching units were placed in close proximity, but electronically separated by a sp³ center. The azobenzene switches were prepared by Baeyer–Mills coupling as key step. The isomerization behavior was investigated by ¹H NMR spectroscopy, UV/Vis spectroscopy, and HPLC. It was shown that all azobenzene moieties are efficiently switchable. Despite the geometric decoupling of the chromophores, computational studies revealed excitonic coupling effects between the individual azobenzene units depending on the connectivity pattern due to the different transition dipole moments of the π→π* excitations. Transition probabilities for those excitations are slightly altered, which is also revealed in their absorption spectra. These insights provide new design parameters for combining multiple photoswitches in one molecule, which have high potential as energy or information storage systems, or, among others, in molecular machines and supramolecular chemistry.     

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.     

Synthesis and characterization of dendrons and dendrimers skeleton-constructed with azobenzene moiety

A series of dendrons and dendrimers skeleton-constructed with azobenzene moiety based upon 4-carboxy-4′-(1,2-propanediolether)-azobenzene as an AB₂ monomer, via a convergent approach, proceeding in a repeated stepwise growth manner starting from 4-carboxy-4′-(n-butylether)-azobenzene as a peripheral monomer, were synthesized, and characterized by NMR, FTIR, and MALDI-TOF-MS analysis. Their regular molecular architecture and thus monodispersed molecular weights were confirmed by GPC. The UV-Vis absorbance and ¹H NMR spectrum study indicated that the azobenzene moieties in CHCl₃ solution took fully trans-cis isomerization under UV irradiation, and reversely isomerization back to the trans by visible light irradiation or by heat.     

Synthesis and characterisation of polymethacrylates containing para-, meta- and ortho-monosubstituted azobenzene moieties in the side chain

Three sets of novel side-chain liquid crystalline polymers with monosubstituted azobenzene moieties in the side-chain have been studied. These are poly(p-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PPHABM), poly(m-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PMHABM) and poly(o-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (POHABM). The chemical structure of the monomers was confirmed by ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. The structural characterisation of the polymers was performed by ¹H NMR spectroscopy and gel permeation chromatography, and their phase behaviour and liquid crystalline properties were studied using differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. The results show that the transitional behaviour of side-chain liquid crystalline polymers containing monosubstituted azobenzene moieties depends strongly on the position of the substituent on the azobenzene moiety; for example, the ortho-monosubstituted polymers do not form liquid crystalline phases, but all the para- and meta-monosubstituted polymers exhibit a smectic A phase. Furthermore, the glass transition temperature (T_g ) of the polymers decreases in the order, para > meta > ortho. For the PPHABM and PMHABM polymers the isotropic temperature (T_i ) and liquid crystalline range (ΔT, from T_g to T_i ) are found to be in the order, para > meta, although it is surprising that the associated enthalpy changes in these polymers is the opposite order, meta > para.     

Nanoscale Chemical Imaging of Reversible Photoisomerization of an Azobenzene‐Thiol Self‐Assembled Monolayer by Tip‐Enhanced Raman Spectroscopy

An understanding of the photoisomerization mechanism of molecules bound to a metal surface at the molecular scale is required for designing photoswitches at surfaces. It has remained a challenge to correlate the surface structure and isomerization of photoswitches at ambient conditions. Herein, the photoisomerization of a self‐assembled monolayer of azobenzene‐thiol molecules on a Au surface was investigated using scanning tunneling microscopy and tip‐enhanced Raman spectroscopy. The unique signature of the cis isomer at 1525 cm^?1 observed in tip‐enhanced Raman spectra was clearly distinct from the trans isomer. Furthermore, tip‐enhanced Raman images of azobenzene thiols after ultraviolet and blue light irradiation are shown with nanoscale spatial resolution, demonstrating a reversible conformational change. Interestingly, the cis isomers of azobenzene‐thiol molecules were preferentially observed at Au grain edges, which is confirmed by density functional theory.     

Exploring London Dispersion and Solvent Interactions at Alkyl–Alkyl Interfaces Using Azobenzene Switches

Interactions on the molecular level control structure as well as function. Especially interfaces between innocent alkyl groups are hardly studied although they are of great importance in larger systems. Herein, London dispersion in conjunction with solvent interactions between linear alkyl chains was examined with an azobenzene‐based experimental setup. Alkyl chains in all meta positions of the azobenzene core were systematically elongated, and the change in rate for the thermally induced Z→E isomerization in n‐decane was determined. The stability of the Z‐isomer increased with longer chains and reached a maximum for n‐butyl groups. Further elongation led to faster isomerization. The origin of the intramolecular interactions was elaborated by various techniques, including ¹H NOESY NMR spectroscopy. The results indicate that there are additional long‐range interactions between n‐alkyl chains with the opposite phenyl core in the Z‐state. These interactions are most likely dominated by attractive London dispersion. This work provides rare insight into the stabilizing contributions of highly flexible groups in an intra‐ as well as an intermolecular setting.     

Surface organization, light-driven surface changes, and stability of semifluorinated azobenzene polymers

A series of polymers with 4-perfluoroalkyl-modified azobenzene side groups was investigated for its light-induced changes in surface properties. The ultraviolet (UV) light activated trans to cis isomerization of the azobenzene group, and the influence of molecular order and orientation on this process were studied using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and water contact angle measurements. Light-induced molecular reorganization in the near-surface region was studied by NEXAFS using in situ UV irradiation of polymer thin films. Differential scanning calorimetry and wide-angle X-ray scattering studies showed that sufficiently long fluoroalkyl groups formed well-ordered smectic mesophases in the bulk, as well as on the surface, which was evidenced by NEXAFS. The disruption of mesogen packing by photoisomerization was found to be influenced by the fluoroalkyl segment length. Surfaces with perfluorohexyl and perfluorooctyl groups that showed high orientational order were also highly resistant to light-induced changes. In such cases, the trans-cis isomerization resulted in greater lowering of the azobenzene phenyl ring order parameters than the perfluoroalkyl order parameters. UV exposure caused reorientation of the phenyl rings of the azobenzene group, but the terminal perfluoroalkyl segments remained more or less ordered.     

Controlling the Surface Functionalization of Ultrasmall Gold Nanoparticles by Sequence-Defined Macromolecules

Ultrasmall gold nanoparticles (diameter about 2 nm) were surface-functionalized with cysteine-carrying precision macromolecules. These consisted of sequence-defined oligo(amidoamine)s (OAAs) with either two or six cysteine molecules for binding to the gold surface and either with or without a PEG chain (3400 Da). They were characterized by ¹H NMR spectroscopy, ¹H NMR diffusion-ordered spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and high-resolution transmission electron microscopy. The number of precision macromolecules per nanoparticle was determined after fluorescent labeling by UV spectroscopy and also by quantitative ¹H NMR spectroscopy. Each nanoparticle carried between 40 and 100 OAA ligands, depending on the number of cysteine units per OAA. The footprint of each ligand was about 0.074 nm² per cysteine molecule. OAAs are well suited to stabilize ultrasmall gold nanoparticles by selective surface conjugation and can be used to selectively cover their surface. The presence of the PEG chain considerably increased the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles.     

Multistimuli‐Responsive Supramolecular Assembly of Cucurbituril/Cyclodextrin Pairs with an Azobenzene‐Containing Bispyridinium Guest

A linear supramolecular architecture was successfully constructed by the inclusion complexation of α‐cyclodextrin with azobenzene and the host‐stabilized charge‐transfer interaction of naphthalene and a bispyridinium guest with cucurbit[8]uril in water, which was comprehensively characterized by ¹H NMR spectroscopy, UV/Vis absorption, fluorescence, circular dichroism spectroscopy, dynamic laser scattering, and microscopic observations. Significantly, because it benefits from the photoinduced isomerization of the azophenyl group and the chemical reduction of bispyridinium moiety with noncovalent connections, the assembly/disassembly process of this supramolecular nanostructure can be efficiently modulated by external stimuli, including temperature, UV and visible‐light irradiation, and chemical redox.     

Synthesis and properties of new ionic liquid crystals based on para-nitroazobenzene with substitution vinylimidazolium ion group

A new series of ionic liquid crystals (ILCs), 1-(4-(4-nitrophenylazo)phenyloxy) vinyl-3-methyl-1H-imidazol-3-ium bromide salts (C _n , n?=?6, 10) were synthesised. Their chemical structures were determined by ¹H NMR, ¹³C NMR, UV spectroscopy and elemental analysis. The liquid crystalline properties were investigated by differential scanning calorimetry, polarising optical microscopy, and powder X-ray diffraction. These measurements showed that C _n (n?=?6, 10) exhibit smectic liquid crystalline phases with focal-conic fan-shaped textures. The introduction of vinylimidazolium group onto the azobenzene enhances the thermal stability of the smectic state, which play an important role in forming the smectic layer structure.     

Design,synthesis, and characterization of a combined main-chain/side-chain liquid-crystalline polymer based on ethyl cellulose

A novel combined main-chain/side-chain liquid-crystalline polymer based on an ethyl cellulose main chain containing azobenzene mesogens (AzoEC) was successfully synthesized. Molecular characterization of the resulting polymers with different degrees of substitution (DS) was performed with proton nuclear magnetic resonance (¹H NMR), Fourier-transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Thermal stability was investigated by thermogravimetric analysis (TGA). The phase transitions and liquid-crystalline behavior of these polymers were investigated by differential-scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The results indicate that DS has substantial effect on the liquid-crystalline behavior of these polymers. AzoEC with low DS only shows the cholesteric phase similar to ethyl cellulose (EC). However, when DS increases to a specific value, AzoEC begins to show fascinating supramolecular structures. The supramolecular structure of AzoEC with maximum DS consisted of a large-scale ordered lamellar structure formed by EC main chains and a small-scale ordered structure formed by azobenzene mesogens.     

4,5-Bis(diphenylthiophosphinoyl)-1,2,3-triazolate interaction with gold nanoparticles and flat surfaces to form self-assembled monolayers

The interaction of the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate (SPTz⁻) with different gold surfaces was investigated (nanoparticles, an electrode, and flat sheets). Studies on binding affinity of this dithiophosphin-triazolate on a gold electrode were performed by cyclic voltammetry (CV). Voltammograms exhibit two reductive desorption and only one oxidative readsorption, indicating that once reabsorbed, the molecule achieves a unique conformation. The morphology and average size of modified gold nanoparticles were studied by transmission electron microscopy (TEM) (av. diameter of 5.9 ± 1.8 nm). Further characterization was made by UV-visible (UV-vis) spectroscopy showing surface plasmon resonance (SPR) at about 580 nm. The bonding configurations of SPTz⁻ on gold have also been investigated by comparing the FT-IR and FT-Raman spectra. The ³¹P{¹H} NMR spectrum of capped nanoparticles exhibited two sharp signals at 30.3 and 29.6 ppm and a very broad signal at 72.7 ppm. X-ray photoelectron spectroscopy (XPS) showed SPTz⁻ can accomplish a strong interaction with gold nanoparticles through bonds involving a sulfur atom and a nitrogen from the triazole ring with a free terminal PS group, forming self-assembled monolayers (SAM). This may allow subsequent functionalization through free S/N atoms of the formed SAMs. The SPTz⁻ packing led to a reduction in packing density that permits large spaces between adsorbed headgroups and the inclusion of carbon and oxygen impurities from small molecules; nevertheless, oxidized sulfur or nitrogen species were not detected, indicating the chemical stability of the obtained SAMs.     

Study on self-assembled monolayers of functionalized azobenzene thiols on gold: XPS,electrochemical properties,and surface-enhanced Raman spectroscopy

Self-assembled monolayers (SAMs) of 4-acetamino-4'-(4-mercaptobutoxy)azobenzene (CH3)CONH-ph-N=N-ph-O(CH2)(4)SH, abbr. aaAzoC4SH) and 4-mercaptobutoxy azobenzene (ph-N=N-ph-O(CH2)(4)SH, abbr. AzoC4SH) on a gold surface have been studied by X-ray photoelectron spectroscopy (XPS), FT Raman spectroscopy, and electrochemistry. A surface-enhanced Raman scattering (SERS)-active system with a "sandwiched" structure of Ag/R-Azo-C4S-/Au was conveniently obtained by the method of Tollen's test. The relationship between the SERS effect and the structural nature of the system indicates that the enhancement correlates to both the silver islands above and the gold substrate underneath. The redox behaviors of the self-assembly on gold electrodes showed that the SAMs of the two compounds exhibit well-behaved voltammetric responses in a Britton-Robinson buffer corresponding to the irreversible two-electron, two-proton reduction-oxidation of azobenzene. The apparent electron-transfer rate kinetics is very sluggish, and the rate constant k(app) of aaAzoC4SH/Au (1.34 x 10(-6) s(-1)) is lower than that of AzoC4SH/Au (1.63 x 10(-4) s(-1)), which may be attributed to the different spatial restriction of close-packing structures on the conformational change accompanied by electron and proton transfer in the SAMs.     

偶氮苯衍生物自组装单分子膜中的分子取响

利用反射红外光谱研究了金表面一系列具有不同碳链长度的偶氮苯巯基衍生物的自组装单分子膜.通过对比各向同性样品的透射谱和单分子膜的反射谱中各个吸收峰强度,定量地研究了分子中各部分的取向与分子结构的关系.我们分别提出了烷基链和偶氮基团取向计算的方法,利用该方法成功地求得了分子中各部分在膜的倾角.结果显示,当分子中烷基链长度增大时,碳链和偶氮苯基团相对于法线的倾斜逐渐加剧.这种倾角的变化归因于分子中碳链间范德华引力增大时,引起分子逐渐倾斜以达到最佳的范德华接触.同时研究发现,烷基链和偶氮基团受碳长度变化的影响并不相同.当分子中亚甲基数目增多时,烷基链的倾角迅速增大而偶氮苯倾角的增大则相对缓慢,这反映了它们在空间需求和本身刚性上的不同。     

Photoresponsive Formation of an Intermolecular Minimal G‐Quadruplex Motif

The ability of three different bifunctional azobenzene linkers to enable the photoreversible formation of a defined intermolecular two‐tetrad G‐quadruplex upon UV/Vis irradiation was investigated. Circular dichroism and NMR spectroscopic data showed the formation of G‐quadruplexes with K⁺ ions at room temperature in all three cases with the corresponding azobenzene linker in an E conformation. However, only the para–para‐substituted azobenzene derivative enables photoswitching between a nonpolymorphic, stacked, tetramolecular G‐quadruplex and an unstructured state after E–Z isomerization.     

Light-Responsive Oligothiophenes Incorporating Photochromic Torsional Switches

We present a quaterthiophene and sexithiophene that can reversibly change their effective π-conjugation length through photoexcitation. The reported compounds make use of light-responsive molecular actuators consisting of an azobenzene attached to a bithiophene unit by both direct and linker-assisted bonding. Upon exposure to 350 nm light, the azobenzene undergoes trans-to-cis isomerization, thus mechanically inducing the oligothiophene to assume a planar conformation (extended π-conjugation). Exposure to 254 nm wavelength promotes azobenzene cis-to-trans isomerization, forcing the thiophenic backbones to twist out of planarity (confined π-conjugation). Twisted conformations are also reached by cis-to-trans thermal relaxation at a rate that increases proportionally with the conjugation length of the oligothiophene moiety. The molecular conformations of quaterthiophene and sexithiophene were characterized by using steady-state UV-vis spectroscopy, X-ray crystallography and quantum-chemical modeling. Finally, we tested the proposed light-responsive oligothiophenes in field-effect transistors to probe the photo-induced tuning of their electronic properties.     

Synthesis and Characterization of Soluble Aromatic Polyesters with Side-Chain Azobeneze and Azothiazole Chromophores

The paper presents the synthesis of a series of polyesters containing nitro-substituted phenyl azothiazole, azobenzothiazole and azobenzene chromophores and their characterization by ¹H NMR, FTIR and UV–Vis spectroscopy. Also the solubility, glass transition temperatures, thermal stability of the synthesized polyesters as well as the surface morphology of thin films of the polyesters were studied.