Synthesis of two naphthyl-containing homologous series of mesogenic ligands and the related metallomesogens containing Cu(II)

Two new naphthyl-containing homologous series of mesogenic ligands, the 4-n-alkoxy-2-hydroxybenzylidene-2'-naphthylamines (series I) and 4(4'-n-alkoxybenzoyloxy)-2-hydroxybenzylidene-2'-naphthylamines (series II), as well as the related metallomesogens of higher homologues containing a Cu(II) atom, have been synthesized. All the ligands and complexes were characterized by a combination of elemental analysis and standard spectroscopic methods. In series I, n-heptyloxy and n-octyloxy derivatives are non-mesogenic whereas the remaining higher members synthesized exhibit a monotropic nematic mesophase. In series II, all the members synthesized exhibit an enantiotropic nematic mesophase. All the metallomesogens of series I synthesized exhibit a monotropic smectic A mesophase, except for the n-octyloxy derivative, which is non-mesogenic, whereas metallomesogens of series II exhibit enantiotropic nematic mesophases up to the n-tetradecyloxy derivatives; the n-tetradecyloxy and n-hexadecyloxy derivatives also exhibit smectic C mesophases. All the members of series II and their metallomesogens exhibit mesophases with wide temperature ranges and greater thermal stability as compared to series I and their metallomesogens, respectively. The mesomorphic properties of both the present series and their metallomesogens are compared with each other and with other structurally related series to evaluate the effect of the naphthalene moiety on mesomorphism.     

My 20 years of research in the chemistry of metal containing liquid crystals

Twenty years ago, in 1977, I began, with important exterior collaborations, original research on metal containing liquid crystals, also known as metallomesogens. I wished to synthesize in this paper my 20 years of research in this field. These compounds combine the known properties of organic liquid crystals with those introduced by the presence of one or more metals (colour, magnetism, polarizability, multiple localized charges) and provide new geometrical shapes including square planar, octahedral, square pyramidal, lantern structures which are unobtainable in purely organic compounds. We have synthesized both rod-like and disc-like metallomesogens, and observed examples of almost all the main mesophase types. In 1977 was the beginning of a systematic research into metallomesogens, the phenomenal growth occurred in early 1980, when many laboratories entered the field.     

A new form of discotic metallomesogens: the synthesis of metal-bridged triphenylene discotic dimers

Discotic metallomesogens are becoming increasingly important due to their electronic and optoelectronic properties. Preliminary results on the synthesis and characterization of a new form of discotic metallomesogens in which a Hg atom is covalently linked with two substituted triphenylene moieties are presented.     

A new form of discotic metallomesogens: the synthesis of metal-bridged triphenylene discotic dimers

Discotic metallomesogens are becoming increasingly important due to their electronic and optoelectronic properties. Preliminary results on the synthesis and characterization of a new form of discotic metallomesogens in which a Hg atom is covalently linked with two substituted triphenylene moieties are presented.     

Metallomesogens: Metal Complexes in Organized Fluid Phases

Metallomesogens, metal complexes of organic ligands which exhibit liquid crystalline (mesomorphic) character, combine the variety and range of metal-based coordination chemistry with the extraordinary physical properties exhibited by liquid crystals. Thermotropic metallomesogens have been made incorporating many metals, including representatives of s-, p-, d-and even f-block elements. Both rodlike (calamitic) and disklike (discotic) thermotropic metallomesogens are known, and examples of all the main mesophase types are found. Many different varieties of ligand can be used: monodentate (4-substituted pyridines), bidentate (β-diketonates, dithiolenes, carboxylates, cyclometalated aromatic amines), or polydentate (phthalocyanines, porphyrins). As with organic mesogens, molecular shape and intermolecular forces play an important role, i.e. the ligands are important in determining mesophase character. The chief requirement for a metallomesogen is a rigid core, usually unsaturated and either rod- or disklike in shape, bearing several long hydrocarbon tails. The metal atom is usually at or near the center of gravity of the molecule. In some cases the ligands are themselves mesogenic, but this is not a requirement. The presence of one or more metals opens many exciting possibilities: new shapes, not easily generated by organic compounds, and hence new properties are then accessible. The incorporation of d-block metals brings with it features such as color and paramagnetism. Profound effects arise from the large and polarizable concentration of electron density that every metal atom possesses, since the molecular polarizability is a key factor in determining whether a molecule will form liquid crystals. Enhanced physical properties (e.g. high birefringencies), as well as new and unexpected ones, will result. A major requirement for metallomesogens to find applications in new device technology is that the metal–ligand bonds are strong and inert and the complexes stable; this can be accomplished with, for example, chelating ligands and the 5d metals.     

New metallomesogens with enaminoketonato ligands

Several metallomesogens based on enaminoketonato ligands have been prepared. 1-Amino-1-(4'-butoxy-4-biphenyl)oct-1-en-3-one was synthesized by heterocycle hydrogenolysis in 3-(4'-butoxy-4-biphenyl)-5-amyl-isoxazole. Liquid crystalline complexes were obtained by reaction of this enaminoketone with nickel(II) or copper(II) acetates. Hydrogenolysis of the heterocycle in 3-(4-hydroxyphenyl)-5-amylisoxazole led to 1-amino-1-(4-hydroxyphenyl)oct-1-en-3-one. The corresponding copper(II) enaminoketonate was then obtained. The subsequent reaction of this compound with 4-alkoxy-benzoic acid chlorides gave liquid crystalline complexes with ester bridges in the core. A nematic phase was observed for all the synthesized metallomesogens. The bridging group influence on melting points, mesophase ranges and thermal stability of copper(II)complexes is discussed.     

Polynuclear Silver(I) Triazole Complexes: Ion Conduction and Nanowire Formation in the Mesophase

Examples of polynuclear metallomesogens are few. Herein,1,2,4‐triazole ligands were used to prepare mono‐ and polynuclear silver(I) triazole metallomesogens. Besides showing an SmA phase in the mesophase, two interesting properties were observed. First, higher ion conductivity is always found for the polynuclear complexes than for the mononuclear complexes with the same anion, an observation contrary to the knowledge that migration of a monomeric cation should be faster than that of a polymeric cation. Second, thermolysis of the polynuclear silver(I) triazole complexes in the assembled mesophase yielded Ag nanowires, in an excellent demonstration of the assembled nature of the polynuclear silver(I) ions in the thermolysis process.     

Thermotropic mesomorphism in penta- and hepta-coordinated metal complexes

New Ni(II) and UO₂(II) metallomesogens obtained from mesomorphic N,N'-salicyliden(3,3'-diamine-N-methyldipropylamine) ligands containing a pentadentate N₃O₂ chelating cavity and bearing two or four lateral substituents, are isolated and fully characterized. Some of the synthesized nickel and dioxouranium complexes show a SmC mesophase. To the best of our knowledge, these species are the first pentacoordinated Ni(II) and heptacoordinated UO₂(II) metallomesogens to be reported.     

Supramolecular metallomesogens. Self-organization of an H-bonded tetrameric assembly into columnar phase from single component

The first example of supramolecular metallomesogens derived from palladium complexes exhibiting columnar phase is reported, and the formation of the mesophase is induced by H-bonding in a tetrameric assembly.     

Listening to Lanthanide Complexes: Determination of the Intrinsic Luminescence Quantum Yield by Nonradiative Relaxation

The photophysical properties of lanthanide complexes have been studied extensively; however, fundamental parameters such as the intrinsic quantum yield as well as radiative and nonradiative decay rates are difficult or even impossible to measure experimentally. Herein, a photoacoustic (PA) method is proposed to determine the intrinsic quantum yield of lanthanide complexes with lifetimes in the order of milliseconds. This method is used to determine the intrinsic quantum yields for europium(III)‐containing metallomesogens as well as terbium(III) complexes. The results show that the PA signal is sensitive to both the lifetime and the ratio of the fast‐to‐slow heat component of the samples. It is found that there is an efficient ligand sensitization and a moderate intrinsic quantum yield for the complexes. The intrinsic quantum yield of Eu³⁺ in the metallomesogens exhibits an obvious increase upon the isotropic liquid to smectic A transition. The proposed PA method is quite simple, and can contribute to a clearer understanding of the photophysical processes in luminescent lanthanide complexes.     

Novel monofunctionalized electron-deficient anthraquinone-based discotic liquid crystals

A series of electron-deficient 1-hydroxy-2,3,5,6,7-pentaalkoxyanthra-9,10-quinones has been synthesized. All nine members of the series were found to be liquid crystalline, forming columnar mesophases over a broad temperature range. Such supramolecular building blocks can be used for the preparation of novel discotic dimers, oligomers, polymers and metallomesogens.     

Synthesis and characterization of cholesterol-based nonsymmetric dimers terminated with ferrocenyl core

The molecular design, synthesis, and thermal behavior of cholesterol-based nonsymmetric dimers, which can also be regarded as metallomesogens, consisting of either two- or three-ring aromatic cores terminated with ferrocenyl unit are reported. The spacer length connecting the cholesterol and aromatic cores is held constant while the length of the spacer connecting ferrocene and aromatic cores has been varied. The occurrence of the enantiotropic mesomorphism in these compounds has been adjudged by optical, calorimetric, and X-ray diffraction studies. In particular these systems exhibit liquid crystal phases such as chiral nematic, twist grain boundary, and smectic A phases. Of these, the chiral nematic phase commonly occurs in all the synthesized compounds.     

孔雀石绿-KIO4催化动力学光度法测定痕量钌

在H2SO4介质中及80 ℃的条件下, 钌对KIO4氧化孔雀石绿的褪色反应有明显催化作用, 探讨了反应的最佳条件, 据此建立了催化动力学光度法测定钌的新方法. 非催化反应吸光度A0与催化反应吸光度A之间的差值ΔA与Ru(Ⅲ)质量浓度在0.1～1.5 μg/25 mL范围内具有良好的线性关系, 检出限为4.31×10-10 g/mL. 测定了动力学参数, 反应为准一级反应, 表观速率常数为3.52×10-4 s, 表观活化能为46.97 kJ/mol. 该方法用于分子筛样品及活性炭样品中痕量钌的测定, 其回率在98.6%～104.8%之间, 符合痕量分析的要求.     

Exploiting soft and hard X-ray absorption spectroscopy to characterize metallodrug/protein interactions: the binding of [trans-RuCl4(Im)(dimethylsulfoxide)][ImH] (Im = imidazole) to bovine serum albumin

The reaction of bovine serum albumin (BSA) with [ trans-RuCl 4(Im)(dimethylsulfoxide)][ImH] (Im = imidazole) (NAMI-A), an experimental ruthenium(III) anticancer drug, and the formation of the respective NAMI-A/BSA adduct were investigated by X-ray absorption spectroscopy (XAS) at the sulfur and chlorine K-edges and at the ruthenium K- and L 3-edges. Ruthenium K and L 3-edge spectra proved unambiguously that the ruthenium center remains in the oxidation state +3 after protein binding. Comparative analysis of the chlorine K-edge XAS spectra of NAMI-A and NAMI-A/BSA, revealed that the chlorine environment is greatly perturbed upon protein binding. Only modest changes were observed in the sulfur K-edge spectra that are dominated by several protein sulfur groups. Overall, valuable information on the nature of this metallodrug/protein adduct and on the mechanism of its formation was gained; XAS spectroscopy turns out to be a very suitable method for the characterization of this kind of systems.     

Theoretical study on photooxidation mechanism of ruthenium complex [Ru(II)‐(bpy)2(TMBiimH2)]2+ with molecular oxygen

Photoinduced reactions of ruthenium complexes with molecular oxygen have attracted a lot of experimental attention; however, the reaction mechanism remains elusive. In this work, we have used the density functional theory method to scrutinize the visible‐light induced photooxidation mechanism of the ruthenium complex [Ru(II)‐(bpy)₂(TMBiimH₂)]²⁺ (bpy: 2, 2‐bipyridine and TMBiimH₂: 4, 5, 4, 5‐tetramethyl‐2, 2‐biimidazole) initiated by the attack of molecular oxygen. The present computational results not only explain very well recent experiments, also provide new mechanistic insights. We found that: (1) the triplet energy transfer process between the triplet molecular oxygen and the metal‐ligand charge transfer triplet state of the ruthenium complex, which leads to singlet molecular oxygen, is thermodynamically favorable; (2) the singlet oxygen addition process to the S₀ ruthenium complex is facile in energy; (3) the chemical transformation from endoperoxide to epidioxetane intermediates can be either two‐ or one‐step reaction (the latter is energetically favored). These findings contribute important mechanistic information to photooxidation reactions of ruthenium complexes with molecular oxygen. © 2016 Wiley Periodicals, Inc.     

Ruthenium dihydride complexes as enyne metathesis catalysts

Ruthenium–catalyzed enyne metathesis is a reliable and efficient method for the formation of 1,3-dienes, a common structural motif in synthetic organic chemistry. The development of new transition-metal complexes competent to catalyze enyne metathesis reactions remains an important research area. This report describes the use of ruthenium (IV) dihydride complexes with the general structure RuH₂Cl₂(PR₃)₂ as new catalysts for enyne metathesis. These ruthenium (IV) dihydrides have been largely unexplored as catalysts in metathesis-based transformations. The reactivity of these complexes with 1,6 and 1,7-enynes was investigated. The observed reaction products are consistent with the metathesis activity occurring through a ruthenium vinylidene intermediate.     

One-dimensional iron(II) compounds exhibiting spin crossover and liquid crystalline properties in the room temperature region

A novel series of 1D Fe(II) metallomesogens have been synthesized using the ligand 5-bis(alkoxy)- N-(4 H-1,2,4-triazol-4-yl)benzamide (C n -tba) and the Fe(X) 2. sH 2O salts. The polymers obey the general formula [Fe(C n -tba) 3](X) 2. sH 2O [X = CF 3SO 3 (-), BF 4 (-); n = 4, 6, 8, 10, 12]. The derivatives with n = 4, 6 exhibit spin transition behavior like in crystalline compounds, whereas those with n = 8, 10, 12 present a spin transition coexisting with the mesomorphic behavior in the room-temperature region. A columnar mesophase has been found for the majority of the metallomesogens, but also a columnar lamellar mesophase was observed for other derivatives. [Fe(C 12-tba) 3](CF 3SO 3) 2 represents a new example of a system where the phase transition directly influences the spin transition of the Fe(II) ions but is not the driving energy of the spin crossover phenomenon. The compounds display drastic changes of color from violet (low-spin state, LS) to white (high-spin state, HS). The compounds are fluid, and it is possible to prepare thin films from them.     

Novel monofunctionalized electron-deficient anthraquinone-based discotic liquid crystals

A series of electron-deficient 1-hydroxy-2,3,5,6,7-pentaalkoxyanthra-9,10-quinones has been synthesized. All nine members of the series were found to be liquid crystalline, forming columnar mesophases over a broad temperature range. Such supramolecular building blocks can be used for the preparation of novel discotic dimers, oligomers, polymers and metallomesogens.     

A self-catalytic role of methanol in PNP-Ru pincer complex catalysed dehydrogenation

Extracting hydrogen from methanol is a safe and cost-efficient strategy for fuel supply. This process was realized recently at a mild condition with excellent efficiency by ruthenium pincer catalysts. Despite the experimental success, the associated mechanism remains under debate. With the aid of density functional theory (DFT) calculations, an updated and self-consistent mechanism which involves MeOH-catalysed dehydrogenation of ruthenium hydride intermediate and pre-protonation of the pincer ligand was present herein. This mechanism is kinetically favoured over the previously-proposed water- or formicacid-participated ones and more consistent with the optimal experimental condition where strong base and neat methanol solvent are used.     

Monitoring the DNA binding kinetics of a binuclear ruthenium complex by energy transfer: evidence for slow shuffling

The semirigid binuclear ruthenium complex Delta,Delta-[mu-(11,11'-bidppz)(phen)(4)Ru(2)](4+) has been shown to rearrange slowly from an initial groove-bound nonluminescent state to a final intercalated emissive state by threading one of its bulky Ru(phen)(2) moieties through the DNA base stack. When this complex binds to poly[d(A-T)(2)], a further increase in emission from the complex is observed after completion of the intercalation, assigned to reorganization of the intercalated complex. We here report a study of the threading process in poly[d(A-T)(2)], in which the minor groove binding dye DAPI is used as an energy transfer probe molecule to assess the distribution of ruthenium complex during and also after the actual threading phase. The emission from DAPI is found to change with the same rate as the emission from the ruthenium complex, and furthermore, DAPI does not disturb the binding kinetics of the latter, justifying it as a good probe of both the threading and the reorganization processes. We conclude from the change in the emission from both DAPI and the ruthenium complex with time that DAPI-ruthenium interactions are most pronounced during the process of threading of the complex, suggesting that the complexes are initially threaded slightly anticooperatively and thereafter redistribute along the DNA to reach their thermodynamically most favorable distribution. The final distribution is characterized by a small but significant binding cooperativity, probably as a result of hydrophobic interactions between the complex ions despite their tetravalent positive charges. The mechanism of "shuffling" the complex along the DNA chain is discussed, i.e., whether the ruthenium complex remains threaded (requiring sequential base-pair openings) or if unthreading followed by lateral diffusion within the ionic atmosphere of the DNA and rethreading occurs.