Activation of Anthraquinone's Electrophilicity by Light for a Dynamic C-O Bond.

Coupling of photoswitching with dynamic covalent chemistry enables control of the formation and cleavage of covalent bonds by light irradiation. peri-Aryloxyanthraquinones feature an exclusive ability to switch electrophilicity by interconversion between para- and ana-quinone isomers, which was used for the first time for the implementation of a dynamic C-O bond. Photogenerated ana-isomers undergo a concerted oxa-Michael addition of phenols to give hitherto unknown 4-hydroxy-10,10-diaryloxyanthracen-9-ones. These species were found to be in equilibrium with the corresponding ana-quinones, thus forming a dynamic covalent system of a new type. Withdrawal of the colored ana-quinones from the equilibria by visible light irradiation resulted in two para-quinones with "locked" aryloxy groups.

Preparation, X-ray Characterization, and Reactivity of the Rod-like and Angular Germanium- and Titanium(IV)-Capped Iron(II) Bis-Clathrochelates and Their Mono- and Bis-Capped (Semi)clathrochelate Precursors.

Transmetalation of the bis{triethylantimony(V)}-capped iron(II) tris-α-dioximate with n-butylboronic acid afforded the mixed antimony, boron cross-linked clathrochelate with single reactive antimony(V)-based apical fragment. This macrobicyclic precursor easily underwent the transmetalation reactions with germanium and titanium(IV) alkoxides to give the rod-like and angular FeII2MIV-trinuclear bis-clathrochelates. Those of the aforementioned diantimony(V)-capped complex with 3- and 4-carboxyphenylboronic acids afforded the monoboron-capped iron(II) semiclathrochelates, undergoing a double-cyclization (macrobicyclization) with germanium- and titanium(IV)-based capping agents. The reactions in the low-temperature range unexpectedly gave the stable 2:1 associates, formed by the bridging of two carboxyl-terminated macrobicyclic molecules of the mixed carboxylboron, triethylantimony-capped iron(II) clathrochelate with a triethylantimony(V)-based linker fragment. The obtained complexes were characterized using elemental analysis, MALDI-TOF, 1H and 13C{1H} NMR and UV-vis spectra, and single-crystal XRD experiments. The encapsulated iron(II) ion in their 3D-molecules is situated almost in the center of its FeN6-coordination polyhedron possessing a truncated trigonal-pyramidal geometry. Fe-N distances fall in the range 1.887(7)-1.945(4) Å characteristic of the low-spin iron(II) complexes. The cross-linking titanium and germanium(IV) ions in the corresponding bis-clathrochelate molecules form the octahedral MIVO6-coordination polyhedra, the MIV-O distances of which vary from 1.946(2) to 1.964(2) Å and from 1.879(7) to 1.907(6) Å, respectively.

Cyclization of arylhydrazones of cross-conjugated enynones: synthesis of luminescent styryl-1H-pyrazoles and propenyl-1H-pyrazoles.

Condensation of 1,5-disubstituted pent-1-en-4-yn-1-ones with arylhydrazines in acidified alcohol results mainly in the formation of the corresponding arylhydrazones with traces of the side products of cyclization at the double bond - 1,5-diaryl-3-(arylethynyl)-4,5-dihydro-1H-pyrazoles (pyrazolines). Arylhydrazones are cyclized only by refluxing in high-boiling polar solvents (DMF and ethylene glycol), with the selective formation of 1,5-disubstituted 3-styrylpyrazoles in up to 77-95% yields. Thermodynamically, the cyclization of arylhydrazones at the triple bond is the most preferable pathway, as shown by DFT calculations and preparative synthesis experiments. Thus, we demonstrate that the reactions of arylhydrazines with 1,5-disubstituted pent-1-en-4-yn-1-ones lead to the formation of arylhydrazones and side pyrazoline impurities in a parallel (not consecutive) manner. 2-Hydrazinylpyridine interacts with 1,5-disubstituted pent-1-en-4-yn-1-ones in some other way, giving not pyridinylhydrazones but 2-(5-styryl-3-phenyl-1H-pyrazol-1-yl)pyridines (despite the acidity of the medium). The authors have developed a gram-scale synthesis method for these compounds, which were obtained in up to 60-82% yields. Besides, we have developed the synthesis method for certain styrylpyrazoles, which are quite promising substances for use as fluorescent probes. Their spectral-luminescence characteristics were examined as well as their complexing with Hg2+, Cd2+, and Pb2+ ions.

Coordination Properties of Hydroxyisophthalic Acids: Topological Correlations, Synthesis, Structural Analysis, and Properties of New Complexes.

Hydroxyisophthalic acids are valuable polytopic ligands for the design of functional materials based on coordination polymers due to the variety of charges and coordination modes they possess. Herein, we describe the synthesis, thermal stability, nonlinear optical (NLO) and spectroscopic properties of five novel coordination compounds, [K2 L(H2 O)2 ], [MgL(H2 O)2 ] ⋅ 3H2 O, [CaL(H2 O)3 ], [SrL(H2 O)3 ] ⋅ H2 O, [BaL(H2 O)(H2 O)5 ], and one salt, (NH4 )2 L ⋅ 2H2 O, with 4,5,6-trihydroxyisophthalic acid (H2 L), which has not been tested in assembling crystalline coordination networks before. The peculiarities of the structural organization of the compounds were analyzed and compared with those for other hydroxyisophthalates. The coordination properties of hydroxyisophthalic acids were studied from the topological point of view, and a comparative topological analysis of coordination and H-bonded networks was performed. Structural correlations revealed in this study could be useful for the design of hydroxyisophthalate-based coordination networks, including porous metal-organic frameworks, proton conductors, and NLO materials.

Reactivity of Cross-Conjugated Enynones in Cyclocondensations with Hydrazines: Synthesis of Pyrazoles and Pyrazolines.

The cyclocondensation of cross-conjugated enynones, dienynones, and trienynones (easily available due to low-cost starting compounds) with arylhydrazines leads to the regioselective synthesis of pyrazole derivatives (dihetaryl-substituted ethens, buta-1,3-diens, and hexa-1,3,5-triens) or results in 4,5-dihydro-1H-pyrazoles in good yield. The reaction path is controlled by the character of the substituent in enynone: the pyrazoles are obtained from the reaction of substrates that contain five-membered heteroaromatic substituents with arylhydrazines, and the 4,5-dihydro-1H-pyrazoles are obtained from the reaction of 1,5-diphenylpent-1-en-4-yn-3-one with arylhydrazines consistently. Despite the presence of a substituent, cyclocondensation of 2-hydrazinylpyridine with all of examined cross-conjugated enynones leads to the formation of pyrazoles. The reaction does not require special conditions (temperature, catalyst, inert atmosphere). The cyclocondensation pathways are determined by the electronic effect of an electron-rich five-membered heteroaromatic ring in the substrate. The synthesis allows use of various substituents and functional groups in enynone and hydrazine. The present method features high yields and simplicity of the product purification. The obtained pyrazoles possess fluorescent properties with a quantum yield up to 31%.

Dramatic Effect of A Ring Size of Alicyclic α-Dioximate Ligand Synthons on Kinetics of the Template Synthesis and of the Acidic Decomposition of the Methylboron-Capped Iron(II) Clathrochelates.

Kinetics and thermodynamics of the template synthesis and of the acidic decomposition of the methylboron-capped iron(II) tris-1,2-dioximates-the clathrochelate derivatives of six (nioxime)- and eight (octoxime)-membered alicyclic ligand synthons-were compared. In the case of a macrobicyclic iron(II) tris-nioximate, the plausible pathway of its formation contains a rate-determining stage and includes a reversible formation of an almost trigonal-antiprismatic (TAP) protonated tris-complex, followed by its monodeprotonation and addition of CH3B(OH)2. Thus, the formed TAP intermediate undergoes a multistep rate-determining stage of double cyclization with the elimination of two water molecules accompanied by a structural rearrangement, thus giving an almost trigonal-prismatic (TP) iron(II) semiclathrochelate. It easily undergoes a cross-linking with CH3B(OH)2, resulting in the elimination of H+ ion and in the formation of a macrobicyclic structure. In contrast, the analogous scheme for its macrobicyclic tris-octoximate analog was found to contain up to three initial stages affecting the overall synthesis reaction rate. The rates of acidic decomposition of the above clathrochelates were found to be also affected by the nature of their ribbed substituents. Therefore, the single crystal XRD experiments were performed in order to explain these results. The difference in the kinetic schemes of a formation of the boron-capped iron(II) tris-nioximates and tris-octoximates is explained by necessity of the substantial changes in a geometry of the latter ligand synthon, caused by its coordination to the iron(II) ion, due to both the higher distortion of the FeN6-coordination polyhedra, and the intramolecular sterical clashes in the molecules of the macrobicyclic iron(II) tris-octoximates.

Synthesis, Structure and Electrochemical Properties of Acetamide- and Caprolactam-Containing Silicon Catecholates.

Hexacoordinated heteroligand silicon catecholates, although being prospective as easily soluble compounds with high hydrolytic stability and diverse redox properties, have been insufficiently studied. The transesterification of 1-(trimethoxysilylmethyl)-2-oxohexahydroaze or N-methyl-N-(trimethoxysilylmethyl)acetamide by two equivalents of catechol derivatives in the presence of dicyclohexylamine afforded a series of target compounds in good yield. The complexes were characterized using elemental analysis, FTIR, 1H, 13C and 29Si NMR spectra, X-ray crystallography and cyclic voltammetry. X-ray diffraction confirmed that the silicon atom possesses the octahedral geometry of the SiCO5 polyhedron that remains unchanged in solution as it follows from 29Si NMR data. The compounds demonstrated up to three oxidation waves; and the reduction profile strongly depended on the nature of the substituents on a catecholate anion.

Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents-The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s).

A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their "click" 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28°. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C-H…H-B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C-H…F-B interaction with an adjacent carboranoclathrochelate molecule. The N-H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1H-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal.

Unprecedented Coordination-Induced Bright Red Emission from Group 12 Metal-Bound Triarylazoimidazoles.

Arylazoimidazoles are important dyes which were intensively studied in the past. In contrast, triarylazoimidazoles (derivatives which carry aryl substituents at the imidazole core) received almost no attention in the scientific literature. Here, we report a new family of simple and easily accessible triarylazoimidazole-group 12 metal complexes, which feature highly efficient photo-luminescence emission (Φ up to 0.44). Novel compounds exhibit bright red emission in solution, which could be excited with a visible light.

Coordination Affinity of Cu(II)-Based Silsesquioxanes toward N,N-Ligands and Associated Skeletal Rearrangements: Cage and Ionic Products Exhibiting a High Catalytic Activity in Oxidation Reactions.

An unusual skeletal rearrangement of piperazine into ethylenediamine has been observed for the first time as a result of an attempt to synthesize a piperazine-linked metal-organic framework (MOF) using cage Cu(II),Na-phenylsilsequixane as a potential building block. Instead of the expected "metallasilsesquioxane-based MOF", a Cu6 complex 1 coordinated both by silsesquioxane and ethylenediamine ligands was isolated. An effort to reproduce this result via direct interaction of Cu-phenylsilsequioxane and ethylenediamine surprisingly afforded two other types of complexes, copper-sodium 2 and copper 3 ionic products. Cationic components in both products 2 and 3 are represented by (i) copper and sodium ions (in the case of 2) or (ii) copper ions exclusively (in the case of 3) coordinated by ethylenediamine ligands. Both complexes 2 and 3 include Si6-based condensed silsesquioxane fragments serving as anionic components of the products. Symptomatically, the types of the Si6-frameworks in 2 and 3 are drastically different. More specifically, the Si6 unit in 2 is an unprecedented distorted silsesquioxane skeleton consisting of two condensed tetramembered rings. Structural features of compounds 1-3 were established by single crystal X-ray diffraction. Compound 2 was found to catalyze the oxidation of cyclohexane to cyclohexanol and cyclohexanone with H2O2 (a mixture of these products was obtained after adding PPh3 to the reaction solution) as well as the transformation of cyclohexanol to cyclohexanone under the action of tert-butyl hydroperoxide.