A highly efficient antioxidant based on boron and a Schiff base bridged phenolic diphenylamine: synthesis, crystal structure and thermal and antioxidant properties.

Antioxidants can effectively protect vegetable-oil-based lubricants against oxidative degradation and prolong their service life. A novel compound, (E)-4-({3,5-di-tert-butyl-2-[(diphenylboranyl)oxy]benzylidene}amino)-N-phenylaniline (BSPD) or {2-[(4-anilinophenyl)iminomethyl-κN]-4,6-di-tert-butylphenolato-κO}diphenylboron, C39H41BN2O, was synthesized by a one-pot reaction of the Schiff base bridged phenolic diphenylamine 2,4-di-tert-butyl-6-{N-[4-(phenylamino)phenyl]carboximidoyl}phenol (SPD) with phenylboronic acid. The corresponding single-crystal X-ray study revealed that the B atom in BSPD has a typical tetrahedral geometry, and the N,O-chelated six-membered ring adopts a chair conformation. According to thermogravimetric analysis, the 5% weight-loss temperature of BSPD increases to 328 °C and the 95% weight-loss temperature is up to 414 °C. More importantly, the antioxidant capability of BSPD in vegetable oil is much better than that of commercial antioxidants [diphenylamine (DPA) and 2,6-di-tert-butyl-4-methylphenol (BHT)] and unmodified SPD.

Multifunctional lubricant additive based on difluoroboron derivatives of a diphenylamine antioxidant.

A metal-free and phosphorus-free novel multifunctional additive (E)-4-((3-(tert-butyl)-2-((difluoroboranyl)oxy)-5-((octylthio)methyl)benzylidene)amino)-N-phenylaniline (difluoroboron derivative 4a) was synthesized and characterized. The results show that its antioxidation and tribological properties are better than those of base oil, diphenylamine and zinc dialkyldithiophosphate (ZDDP), and it can also increase the extreme pressure performance of the base oil. In addition, it can be found that the diphenylamine functional group, boron and fluorine are the main contributors to the excellent antioxidation and antiwear properties of difluoroboron derivative 4a, respectively. Finally, the results of X-ray photoelectron spectroscopy on the worn surfaces reveal that B2O3, Fe2O3, a N-containing organic compound and iron fluoride comprise the boundary films, which effectively improve the difluoroboron derivative 4a's antiwear properties.

Facile synthesis of photoluminescent inorganic-organic hybrid carbon dots codoped with B and N: towards an efficient lubrication additive.

A novel environmentally friendly bis-functional dicationic ionic liquid containing chelated orthoborate was synthesized and polycondensed with glutamic acid in order to synthesize inorganic-organic carbon dots (CD/IL) consisting of an ionic liquid moiety inserted in the carbon skeleton. The obtained CD/IL was found to be a new kind of nitrogen/boron-codoped nanomaterial, one with a mean particle diameter of 2.66 nm. CD/IL was verified to be a high-performance lubricant additive: in particular, the anti-wear and friction-reducing properties of poly(ethylene glycol) (PEG) were improved by 89.34% and 62.18%, respectively, when 1% CD/IL was added. Lubricants consisting of a mixture of CD/IL and PEG showed intense blue photo-fluorescence, and the corresponding photoluminescence (PL) intensity decreased considerably after carrying out a tribo-test. Moreover, CD/IL became transferred onto a rubbing steel interface during the tribo-test according to EDX and Raman analyses of a worn surface. CD/IL showed poor crystallinity, and interestingly, an intense G (∼1600 cm-1) signature was detected on the steel surface after a high-load and long-duration tribo-test, which indicated that ordered carbon materials were generated on the interface, inhibiting the undesirable wear.

The antioxidant methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

The title compound, C18H28O3, was prepared by the reaction of 2,6-di-tert-butylphenol with methyl acrylate under basic conditions using dimethyl sulfoxide as the promoter. The structure of this antioxidant indicates significant strain between the ortho tert-butyl substituents and the phenolic OH group. In spite of the steric crowding of the OH group, it participates in intermolecular hydrogen bonding with the ester carbonyl O atom.

Reactivity of [1(2,3)4]pentamantane (Td-pentamantane): a nanoscale model of diamond.

To model the chemical properties of the hydrogen-terminated nanodiamond {111} and {110} surfaces, the functionalizations of the higher diamondoid [1(2,3)4]pentamantane were studied. [1(2,3)4]Pentamantane reacts selectively with neat bromine to give the medial 2-mono- and 2,4-disubstitution products. In contrast, oxidation with nitric acid as well as single-electron-transfer oxidation involving the [1(2,3)4]pentamantane radical cation results in apical C7-substitutions. This substitution pattern dominates in the free-radical bromination under phase-transfer catalytic conditions that gives a mixture of 7- and 2-bromo[1(2,3)4]pentamantane in a 95:5 ratio. Replacement of the functional groups in [1(2,3)4]pentamantane occurs without isomerization. This was demonstrated for the interconversions of the bromo and hydroxy derivatives as well as for the preparation of [1(2,3)4]pentamantyl-7-thiol from 7-hydroxy[1(2,3)4]pentamantane. Thus, the selective functionalization of hydrogen-terminated nanodiamonds is possible by means of reactions with common electrophiles-oxidizers.

Control over charge separation in phthalocyanine-anthraquinone conjugates as a function of the aggregation status.

We have prepared three isomeric donor-acceptor systems, in which two phthalocyanine (Pc) units have been attached to the 1-,5- (1a), 1-,8- (1b), or 2-,6- (1c) positions of a central anthraquinone (AQ) moiety, leading to packed (1b) or extended (1a and 1c) topologies. The electronic interactions between the donor and the acceptor in the ground state or in the excited states have been studied by different electrochemical and photophysical techniques. Due to the markedly different topologies, we have been able to modify these interactions at the intramolecular level and, by a proper choice of the solvent environment, at the intermolecular level within aggregates. In triad 1b, the ZnPc units are forced to pi-stack cofacially and out of the plane of the AQ ring. Consequently, this molecule shows strong inter-Pc interactions that give rise to intramolecular excitonic coupling but a relatively small electronic communication with the AQ acceptor through the vinyl spacers. On the contrary, the 1-,5- or 2-,6-connections of triads 1a and 1c allow for an efficient pi-conjugation between the active units that extends over the entire planar system. These two molecules tend to aggregate in aromatic solvents by pi-pi stacking, giving rise to J-type oligomers. Photoexcitation of the Pc units of 1a-c results in the formation of the Pc.+-AQ.- charge transfer state. We have demonstrated that the kinetics of these electron transfer reactions is greatly dependent on the aggregation status of the triads.

Functionalized nanodiamonds: triamantane and [121]tetramantane.

The selective functionalizations of the fundamental hydrogen-terminated nanodiamonds triamantane 1, as well as the most symmetrical representative of the tetramantanes (C(2h)-[121]tetramantane 2) were elaborated. Electrophilic reagents (Br2, HNO3) predominantly attack the medial C-H positions of the cages; bromination of 2 gave the medial 2-bromo derivative almost exclusively. Highly selective apical substitution in 1 and 2 is possible either under single-electron-transfer oxidations via hydrocarbon radical cations or through photoacetylation with diacetyl. The mono- and the bis-acetyl derivatives of 1 and 2 were converted through Bayer-Villiger oxidation and subsequent hydrolysis to the respective apical mono- and dihydroxy derivatives. This exceptional synthetic specificity facilitates the transformation of 2, and perhaps larger nanodiamond molecules, into functionalized building blocks needed for a wide range of applications such as nanotechnology.

Functionalized nanodiamonds part 3: thiolation of tertiary/bridgehead alcohols.

[reaction: see text] Treatment of acyclic as well as polycyclic tertiary mono- and dihydroxy hydrocarbon derivatives with thiourea in the presence of hydrobromic and acetic acid represents a convenient one-step route to the respective tertiary thiols and dithiols. This procedure was used for the preparation of diamondoid thiols of diamantane, triamantane, [121]tetramantane, and others that are prospective nanoelectronic materials.

Raman spectroscopy of diamondoids.

A selection of diamondoid hydrocarbons, from adamantane to [121321] heptamantane, have been analysed by multi-wavelength laser Raman spectroscopy. Spectra were assigned using vibrational frequencies and Raman intensities were calculated by employing the B3LYP functional and the split valence basis set of Schafer, Horn and Ahlrichs with polarisation functions on carbon atoms. The variation of the spectra and associated vibrational modes with the structure and symmetry of the molecules are discussed. Each diamondoid was found to produce a unique Raman spectrum, allowing for easy differentiation between molecules. Using the peak assignments derived from the calculations we find that the low frequency region of the spectra, corresponding to CCC-bending/CC-stretching modes, is particularly characteristic of the geometric shape of the diamondoid molecules.

Tuning photoinduced energy- and electron-transfer events in subphthalocyanine-phthalocyanine dyads.

A series of subphthalocyanine-phthalocyanine dyads has been prepared by means of palladium-catalyzed cross-coupling reactions between a monoalkynylphthalocyanine and different monoiodosubphthalocyanines. Electronic coupling between the two photoactive units is ensured by a rigid and pi-conjugated alkynyl spacer. In addition, the electronic characteristics of the subphthalocyanine moiety were modulated by the introduction of different peripheral substituents. Cyclic and Osteryoung square-wave voltammetry experiments revealed that the reduction potential of this subunit can be decreased by about 400 mV on going from thioether or no substituents to nitro groups. As a consequence, the energy level of the charge-transfer state could be fine-tuned so as to gain control over the fate of the photoexcitation energy in each subunit. The diverse steady-state and time-resolved photophysical techniques employed demonstrated that, when the charge-transfer state lies high in energy, a quantitative singlet-singlet energy-transfer mechanism from the excited subphthalocyanine to the phthalocyanine takes place. On the contrary, stabilization of the radical pair by lowering the redox gap between electron donor and acceptor results in a highly efficient photoinduced electron-transfer process, even in solvents of low polarity such as toluene (Phi(ET) approximately 0.9). These features, together with the extraordinary absorptive cross section that these molecular ensembles display across the whole UV/Vis spectrum, make them model candidates for application in situations where broadband light sources are needed.

Evidence of pronounced electronic coupling in a directly bonded fullerene--ferrocene dyad.

A new donor-acceptor dyad (7) involving a ferrocene moiety as donor and an azafullerene as acceptor has been synthesized by treating bisazafullerenyl (1) with ferrocenium hexafluorophosphate. This compound represents the first example of a fullerene-based dyad where two electroactive groups are connected by only a single sigma-bond. The cyclic voltammetry of 7, in comparison to the corresponding reference systems, clearly reveals strong electronic coupling between the ferrocene and the azafullerene moiety in the ground state. For example, the Fc-based, reversible, one electron oxidation wave is significantly positively shifted by 183 mV with respect to that of the parent ferrocene. This indicates the existence of intramolecular charge transfer (ICT) from the donating Fc to the accepting azafullerenyl group. Photophysical studies on 7 were carried out by means of emission and transient absorption spectroscopy. An instantaneous deactivation of the fullerene singlet excited-state results in the formation of the charge-separated (C59N.-)-(Fc.+) radical pair. From the charge-transfer dynamics with a lower limit of > or = 5 x 10(10) s-1, we infer strong electronic coupling (V) between the azafullerene and the ferrocene moiety of the order of 60 cm-1 in benzonitrile.

A New Dyad Based on C(60) and a Conjugated Dimethylaniline-Substituted Dithienylethylene Donor.

A facile synthesis of the title compound is described, and its optical and electrochemical properties are discussed.