Heat-set gel-like networks of lipophilic Co(II) triazole complexes in organic media and their thermochromic structural transitions

A novel class of thermally responsive supramolecular assemblies is formed from the lipophilic cobalt(II) complexes of 4-alkylated 1,2,4-triazoles. When an ether linkage is introduced in the alkylchain moiety, a blue gel-like phase is formed in chloroform, even at very low concentration (ca. 0.01 wt %, at room temperature). The blue color is accompanied by a structured absorption around 580-730 nm, which is characteristic of cobalt (II) in the tetrahedral (T(d)) coordination. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) of the gel-like phase confirms the formation of networks of fibrous nanoassemblies with widths of 5-30 nm. The observed widths are larger than a molecular length of the triazole ligand (ca. 2.2 nm) and they are consisted of aggregates of T(d) coordination polymers. Very interestingly, the blue gel-like phase turned into a solution by cooling below 25 degrees C. A pale pink solution is obtained at 0 degrees C, indicating the formation of octahedral (O(h)) complexes. The observed thermochromic transition is totally reversible. The formation of gel-like networks by heating is contrary to the conventional organogels, which dissolve upon heating. Temperature dependence of the storage and loss moduli (G' and G") shows minima around at 27 degrees C, at which temperature they gave comparable values. On the other hand, G' exceeds G" both in the gel-like phase (temperature above 27 degrees C) and in the solution phase (temperature below 25 degrees C). These observations indicate that T(d) complexes are present as low-molecular weight species around at 25-27 degrees C. They are self-assembled to polymeric T(d) complexes by heating and form gel-like networks. Upon cooling the solution below 25 degrees C, T(d) complexes are converted to O(h) complexes and they also self-assemble into oligomeric or polymeric species at lower temperatures. The observed unique thermochromic transition (pink solution --> blue gel-like phase) is accompanied by an exothermic peak in differential scanning calorimetry (DSC), and is shown to be an enthalpy-driven process. The lipophilic modification of one-dimensional coordination systems provides unique solution properties and it would be widely applicable to the design of thermoresponsive, self-assembling molecular wires.     

Synthesis and transformations of acids of the triazole series

3,5-Di(m- and p-tolyl)-1,2,4-triazples were obtained by reaction of formalin with 2,5-ditolyl-1,3,4-oxadiazoles and subsequent hydrolysis of the resulting formyl derivatives. 3,5-Di(o-tolyl)-1,2,4-triazole cannot be obtained by this method. The oxidation of 3,5-ditolyl-1,2,4-triazoles leads to 3,5-bis(carboxyphenyl)-1,2,4-triazoles, which were converted to diesters and dihydrazides.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 848–849, June, 1978.     

Self-assembling molecular wires of halogen-bridged platinum complexes in organic media. Mesoscopic supramolecular assemblies consisting of a mixed valent Pt(II)/Pt(IV) complex and anionic amphiphiles

A novel class of supramolecular assemblies in organic media consisting of a molecular wire of a halogen-bridged platinum complex [Pt(en)2][PtCl2(en)2]4+ (en = 1,2-diaminoethane) and anionic amphiphiles is developed. When double-chained phosphates or sulfonates are employed, the resultant [Pt(en)2][PtCl2(en)2](4+)-lipid complexes displayed intervalence charge transfer (CT) absorption bands in the crystalline state. They are soluble in organic solvents because of the amphiphilic superstructure, in which the solvophobic one-dimensional platinum complex is surrounded by solvophilic alkyl chains. CT absorption bands of halogen-bridged linear complexes are maintained in organic media, with varied colors that depend on the chemical structure of constituent amphiphiles. Monoalkylated phosphates failed to form colored, halogen-bridged ternary complexes probably because of their coordination to the axial position of PtII(en)2. Formation of mesoscopic supramolecular assemblies in organic media was confirmed for the [Pt(en)2][PtCl2(en)2] complexes by electron microscopy. Interestingly, a supramolecular complex consisting of dihexadecyl sulfosuccinate and [Pt(en)2][PtCl2(en)2]4+ displayed clear, indigo solutions that are distinct from the yellow color observed for those of [Pt(en)2][PtCl2(en)2]/dialkyl phosphate complexes. The indigo color of the former complex disappeared upon heating the solution to 60 degrees C, whereas it reappeared reversibly by cooling the solution to room temperature. In electron microscopy, rodlike nanostructures with a minimum width of 18 nm and lengths of 700-1700 nm were observed after cooling, though not at elevated temperatures. Apparently, the lipid-[Pt(en)2][PtCl2(en)2]4+ complex undergoes reversible dissociation and reassembly processes in chloroform, and it becomes better dispersed after the reassembling process. The present finding opens a general route to solution chemistry of low-dimensional inorganic complexes and enables rational design and control of self-assembling inorganic molecular wires.     

Borohydride complexes of rare earths,and their applications in various organic transformations

Borohydride complexes of the rare earths have attracted increasing interest during the last decade. This review aims to cover recent results over this period with respect to the preparation, characterization, structure, and applications in organic chemistry of this family of compounds, including inorganic and organometallic complexes. Special emphasis is made on their use for polymerization catalysis.     

Aurophilic complexes as gold atom sources in organic media

The decomposition, either thermal or under H2, of [O(AuIPR3)3](CF3SO3) (R = Ph 1, R = Me 2) in organic solvents has been studied by 31P(1H) NMR, UV-vis spectroscopy and TEM; during the reaction, the phosphine acts as an efficient oxygen trap and gold nanoparticles are produced which may be stabilized by PVP in acetonitrile (mean diameter 4.5 nm) or oleylamine in toluene (mean diameter 9 nm).     

Thermochemical studies on organic eutectics and molecular complexes

The phase diagrams of the binary systems of picric acid with naphthalene, anthracene and phenanthrene, and of -naphthol withp-toluidine, determined by the thaw-melt method, show the formation of a molecular complex and two eutectics in each system. The heats of the pure components, eutectics and molecular complexes were determined by differential scanning calorimetry. Comparison of the experimental heats of fusion with the theoretical values calculated via the mixture law suggests cluster formation in the melts. The entropy of fusion, enthalpy of mixing and excess thermodynamic functions were also calculated from the heat of fusion data.

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Zusammenfassung Die Phasendiagramme der binären Systeme von Pikrinsäure mit Naphthalin, Anthrazen und Phenanthren sowie von -Naphthol mit p-Aminotoluol wurden bestimmt. In jedem System zeigt sich die Bildung eines Molekülkomplexes sowie je zwei Eutektika. Mittels DSC wurden die Schmelzwärmen der reinen Komponenten, der eutektischen Mischungen und der Molekülkomplexe ermitteis. Der Vergleich der experimentell ermittelten Schmelzwärmen mit den mittels der Mischungsregel errechneten Werten läßt auf eine Clusterbildung in der Schmelze schließen. Weiterhin wurden aus den Schmelzwärmen auch Werte für Schmelzentropie und Mischungsenthalpie errechnet.

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Thanks are due to Prof. I. S. Ahuja, Head, Chemistry Department, Banaras Hindu University, for providing research facilities. Thanks are also due to CSIR, New Delhi, for financial assistance.     

Chemical transformations of organic sulfides during hydrogenolysis in the presence of metal chloride complexes

Desulfurization of organic sulfides in hydrocarbon solvents in the presence of aqua complexes of metal chlorides H[MAlCl₄OH] that exhibit lower acidity as compared to AlCl₃ proceeds under mild conditions (450–525 K, atmospheric pressure) without external introduction of hydrogen. The process occurs with cleavage of C-S bonds and through intermediate formation of mercaptans to give H₂S and the corresponding hydrocarbons. The reaction is accompanied by cleavage of C-C bonds in the groups surrounding the organosulfur moiety, in thiacyclane rings, as well as in hydrocarbon solvent molecules, resulting in the formation of a wide spectrum of gaseous and liquid products.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1998–2002, October, 1995.     

Ion-dipole effect as a force for molecular recognition in organic media

Neutral macrocycle 1b shows a substantial binding affinity for quaternary ammonium and immonium compounds in chloroform due to ion-dipole attractions.     

Photoresponsive molecular tools for emerging applications of light in medicine

Light-based therapeutic and imaging modalities, which emerge in clinical applications, rely on molecular tools, such as photocleavable protecting groups and photoswitches that respond to photonic stimulus and translate it into a biological effect. However, optimisation of their key parameters (activation wavelength, band separation, fatigue resistance and half-life) is necessary to enable application in the medical field. In this perspective, we describe the applications scenarios that can be envisioned in clinical practice and then we use those scenarios to explain the necessary properties that the photoresponsive tools used to control biological function should possess, highlighted by examples from medical imaging, drug delivery and photopharmacology. We then present how the (photo)chemical parameters are currently being optimized and an outlook is given on pharmacological aspects (toxicity, solubility, and stability) of light-responsive molecules. With these interdisciplinary insights, we aim to inspire the future directions for the development of photocontrolled tools that will empower clinical applications of light.

This perspective article explores the current state of light-controlled molecular tools for medical therapy and imaging and offers an outlook on clinical application scenarios and optimisation strategies.     

Enhanced activity of α-chymotrypsin in organic media using designed molecular staples

We report the enhancement of α-chymotrypsin activity in organic solvents using modified peptides bearing two crown ethers. The transesterification of N-acetyl-l-phenylalanine ethyl ester with 1-propanol was used as model reaction. Co-lyophilization of crown ether modified peptides with α-chymotrypsin prior to use resulted in an increase of enzyme catalytic activity in non-aqueous media. The efficiency of enzyme activation is dependent on the amino acid sequence of peptidic additives and on the positions of the amino acids bearing the crown ligand.     

Controlled polymerization and self-assembly of halogen-bridged diruthenium complexes in organic media and their dielectrophoretic alignment

Lipophilic paddlewheel biruthenium complexes [Ru(2)(μ-O(2)CR)(3)X](n) (O(2)CR = 3,4,5-tridodecyloxybenzoate, X = Cl, I) self-assemble in organic media to form halogen-bridged coordination polymers. The polymerization is accompanied by spectral changes in π(RuO,Ru(2)) → π*(Ru(2)) and π(axial ligand) → π*(Ru(2)) absorption bands. These polymeric complexes form lyotropic liquid crystals in n-decane at concentrations above ~100 unit mM. The bridging halogen axial ligands (X = Cl or I) exert significant influences on their electronic structures and self-assembling characteristics: the chloride-bridged polymers give hexagonally aligned ordered columnar structure (columnar hexagonal phase, Col(h)), whereas the iodide-bridged polymers form less ordered columnar nematic (Col(n)) phase, as revealed by small-angle X-ray diffraction measurements. Chloro-bridged coordination polymers dispersed in n-decane are thermally intact even at the elevated temperature of 70 °C. In contrast, iodo-bridged polymers show reversible dissociation and reassembly phenomena depending on temperature. These halogen-bridged coordination polymers show unidirectional alignment upon applying alternating current (ac) electric field as investigated by crossed polarizing optical microscopy and scanning electron microscopy. The unidirectionally oriented columns of chloro-bridged polymers are accumulated upon repetitive application of the ac voltage, whereas iodo-bridged coordination polymers show faster and reversible alignment changes in response to turning on-and-off the electric field. The controlled self-assembly of electronically conjugated linear complexes provide a potential platform to design electric field-responsive nanomaterials.     

Effect of bond-length alternation in molecular wires

Current-voltage (I-V) characteristics for metal-molecule-metal junctions formed from three classes of molecules measured with a simple crossed-wire molecular electronics test-bed are reported. Junction conductance as a function of molecular structure is consistent with I-V characteristics calculated from extended Hückel theory coupled with a Green's function approach, and can be understood on the basis of bond-length alternation.     

Evidence of four light-induced metastable states in iron-nitrosyl complexes

Thermodynamic measurements on irradiated Na₂[Fe(CN)₅NO]⋅ 2H₂O reveal the existence of four light-induced long-lived metastable states, which decay exponentially in time. The activation energies and frequency factors of the four independent states are determined from isothermal calorimetric and differential scanning calorimetric measurements.     

First metal complexes of 6,6'-dihydroxy-2,2'-bipyridine: from molecular wires to applications in carbonylation catalysis

The first square planar rhodium(I) complexes containing the 6,6'-dihydroxy-2,2'-bipyridine ligand have been prepared. The complexes form molecular wires in the solid state and are active catalysts for the carbonylation of methyl acetate.     

Synthesis of basic molecular brushes: ATRP of 4-vinylpyridine in organic media

A poly(2-(2-bromopropionyloxy)ethyl methacrylate) (PBPEM) was used as macroinitiator in the synthesis of molecular brushes with poly(4-vinylpyridine) side chains, (P(BPEM-g-4VP). Atom transfer radical polymerization (ATRP) was employed as the polymerization technique. The polymerizations were carried out in DMF at 30 °C using a copper-chloride-based ATRP catalyst, which converted all the dormant polymer chain ends to alkyl chloride groups, thus minimizing branching and crosslinking, which occurred when a copper bromide-based catalyst was employed. Tris(2-pyridylmethyl)amine was selected as the ligand due to the high activity of its Cu^I complex in ATRP as well as its strong binding to both Cu^I and Cu^II, which prevented competitive complexation of the monomer or polymer to the metal center. In order to prevent crosslinking via radical coupling, the monomer conversion was kept low (under 3%) and the alkyl chloride end groups of P4VP side chains were converted to alkoxyamines upon activation followed by a reaction with TEMPO radical. Dynamic light scattering measurements showed the hydrodynamic diameter (D_H) of the brushes was pH-dependent. Aggregation of single P(BPEM-g-4VP) brushes in water was very pronounced at high pH values but was observed even when the amount of added HCl was enough to completely protonate the pyridine units (D_H = 278 nm).     

Molybdenum complexes as catalysts for the reduction of molecular nitrogen in protic media

N₂-fixing systems in protic media consisting of different reducing agents and molybdenum complexes (initially Mo(V)) as N₂ activators form the same Mo(III) carbonyl upon replacing N₂ by carbon monoxide. When CO is removed from the carbonyl, the Mo(III) complex formed becomes again capable of catalyzing the reduction of N₂ to hydrazine by Ti(III) or Cr(II) hydroxide in aqueous alcohol. Sodium amalgam forms a particularly active system, reducting N₂ catalytically in the presence of a Mo(III) complex already at room temperature.

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EPR spectroscopy of transformations of iridium(III) and iridium(IV) hydroxo complexes in alkaline media

Processes that occur in strong alkaline solutions of iridium(III) and iridium(IV) hydroxo complexes have been studied by EPR and electronic absorption spectroscopy. It has been demonstrated that dissolution of iridium compounds in alkaline solutions should be accompanied by a series of complicated transformations involving oxygen, which lead to the formation of several binuclear iridium(III, III), (III, IV), and (IV, IV) dioxygen complexes.