A series of heterometallic binuclear [PhenPd-(μ-dmpz)2M-(OOCR)2] (1: M = CuII, R = t Bu; 2: M = CuII, R = Me; 3: M = CuII, R = Ph; 4: M = CoII, R = Ph) and trinuclear [PhenPd2(μ-dmpz)4Zn-(OOCMe)2] (5) 1,10-phenanthroline (Phen)-based complexes was obtained. The complexes were fully characterized by X-ray diffraction, FT-IR spectroscopy, ESI-Mass Spectrometry, NMR spectroscopy, and elemental analysis. According to X-ray diffraction data, palladium atoms in all complexes were in a square-planar environment, while the Zn, Co, and Cu atoms were in a tetrahedral or distorted square-planar environment, with a nonbinding distance of Pd···M ranging from 3.213-3.468 Å. Mass spectrometry data confirmed the integrity of the heterometallic pyrazolate bridging core in solution. These findings provide a rational synthetic approach for the design of heterometallic assemblies with specific compositions and nuclearities.

The reaction of the mononuclear complex [PhenCu(OOCtBu)2(H2O)] (I) with [PhenCu(CH3CN)(Otf)2] (Phen = 1,10-phenanthroline, Otf = CF3S O_3^ - ) in dichloromethane at room temperature gave the binuclear complex [Phen2Cu2(µ-OOCtBu)2(Otf)2] (II). The reaction of II with pyrazole (PzH) involved the displacement of the triflate anions to the outer sphere and gave the ionic complex [Phen2Cu2(µ-OOCtBu)2(PzH)2](Otf)2 (III), while a similar reaction with 3,5-bis(trifluoromethyl)pyrazole ((CF3)2PzH) was accompanied by its deprotonation and gave the heteroleptic complex [Phen2Cu2(µ-OOCtBu)(µ-(CF3)2Pz)(µ-Otf)]Otf (IV). Compounds I–IV were characterized by X-ray diffraction (CCDC nos. 2332399 (I), 2332400 (II), 2332402 (III), and 2332401 (IV)), IR spectroscopy, and elemental analysis. According to X-ray diffraction data, the copper atoms in I–IV occur in a square pyramidal environment. The crystal packing of complexes I–III involves stacking interactions between phenanthroline molecules giving rise to supramolecular chains.

Dinuclear complexes bearing Ru(II) photoactive center are of interest for the development of efficient dual catalysts for many photocatalyzed reactions. Ditopic polypyrine ligands – bis(pyridine-2-yl)amino-1,10-phenanthrolines – containing additional coordination site (bis(pyridine-2-yl)amine, dpa) at positions 3, 4 or 5 of 1,10-phenanthroline core (Phen-3NPy2, Phen-4NPy2 and Phen-5NPy2) were synthesized. They were used as bridging ligands to obtain dinuclear complexes of composition [(bpy)2Ru(Phen-NPy2)PdCl2](PF6)2 (Ru(Phen-NPy2)Pd) via stepvise comlexing in good yields. Ru(II) is coordinated to 1,10-phenanthroline in these complexes, while Pd(II) is bound to dpa chelating moiety, which was established by NMR spectroscopy and X-ray single crystal analysis. The influence of the position of dpa in phenanthroline ring on the structural, optical and electrochemical properties of Ru(Phen-NPy2)Pd complexes was studied. The complexes possess photoluminescence in argon-saturated MeCN solution with maxima in the range of 615–625 nm, emission quantum yields range from 0.11 to 0.15 for Ru(Phen-NPy2) complexes and from 0.018 to 0.026 for dinucear Ru(Phen-NPy2)Pd complexes. All the complexes have high extinction coefficients in the range of 370–470 nm, efficiently absorb visible light and can be used as photocatalysts. The Ru2+/3+ potential in Ru(Phen-NPy2)Pd complexes showed no significant dependence on dpa position, while Pd2+/0 reduction potential was quite lower for Ru(Phen-3NPy2)Pd and Ru(Phen-NPy2)Pd, than for Ru(Phen-NPy2)Pd (–0.57V and –0.72V vs Ag/AgCl, KCl(sat), respectively). The behaviour of the complexes was studied in Сu-free Sonogashira coupling under blue LED (12 W) irradiation. The reaction proceeds three times faster when Ru(Phen-4NPy2)Pd and Ru(Phen-3NPy2)Pd are used as catalysts precursors than in the case of mixed catalytic system Ru(bpy)3(PF6)2/(RNPy2)PdCl2.

Dinuclear complexes bearing Ru(II) photoactive centers are of interest for the development of efficient dual catalysts for many photocatalyzed reactions. Ditopic polypyridine ligands, bis(pyridin-2-yl)amino-1,10-phenanthrolines, containing an additional coordination site (bis(pyridin-2-yl)amine, dpa) at positions 3, 4 or 5 of the 1,10-phenanthroline core (Phen-3NPy2, Phen-4NPy2 and Phen-5NPy2) were synthesized. They were used as bridging ligands to obtain dinuclear complexes [(bpy)2Ru(Phen-NPy2)PdCl2](PF6)2 (Ru(Phen-NPy2)Pd) in good yields via stepwise complexation. In these complexes Ru(II) is coordinated to 1,10-phenanthroline, while Pd(II) is bound to the dpa chelating moiety, as established by NMR spectroscopy and X-ray single crystal analysis. The influence of the position of dpa in the phenanthroline ring on the structural, optical and electrochemical properties of Ru(Phen-NPy2)Pd complexes was studied. The complexes exhibit photoluminescence in argon-saturated MeCN solution with maxima in the range of 615-625 nm, with emission quantum yields ranging from 0.11 to 0.15 for Ru(Phen-NPy2) complexes and from 0.018 to 0.026 for dinuclear Ru(Phen-NPy2)Pd complexes. All the complexes absorb visible light in the range of 370-470 nm with high extinction coefficients and can be considered useful as photocatalysts. The Ru2+/3+ potential in Ru(Phen-NPy2)Pd complexes showed no significant dependence on the dpa position, while the Pd2+/0 reduction potential was significantly lower for Ru(Phen-3NPy2)Pd and Ru(Phen-4NPy2)Pd, than for Ru(Phen-5NPy2)Pd (-0.57 V and -0.72 V vs. Ag/AgCl, KCl(sat.), respectively). The complexes were used as photoactivated precatalysts in Cu-free Sonogashira coupling under blue LEDs (12 W) irradiation. The reaction proceeded roughly three times faster when Ru(Phen-4NPy2)Pd and Ru(Phen-3NPy2)Pd were used as catalyst precursors compared to the mixed catalytic system Ru(bpy)3(PF6)2/(RNPy2)PdCl2.

The unique palladium(ii) complexes, namely, (Phen)Pd((CF3)2pz)2, (Phen)Pd(MeCF3pz)2, and [(Phen)Pd2(μ-dmpz)2(dmpz)(Hdmpz)](OAc)2H, where (CF3)2pzH is 3,5-bis(trifluoro methyl) pyrazole, MeCF3pzH is 3-methyl-5-trifluoro methylpyrazole, Hdmpz is 3,5-dimethyl- pyrazole, Phen is 1,10-phenanthroline, have been obtained by the reactions of (Phen)Pd(OAc)2 with the corresponding free NH-pyrazoles. According to the X-ray data, in the mononuclear pyrazolate complexes the Pdii atom has a square planar environment of nitrogen atoms of phenanthroline and two monodentate-bound pyrazolate anions. The binuclear pyrazolate-bridged complex is additionally stabilized by intramolecular hydrogen bonding of the terminal dmpz anion and Hdmpz.

Using (bis)diethoxyphosphoryl ferrocene [Fc(O 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 P(OEt)2)2] and transition metal carboxylates - [M2(mu-OOCR)4(CH3CN)2], M = CuII, R = tBu, (C5H4)Mn(CO)3 (Cym) or [M3(mu-OOCR)6(CH3CN)2], M = NiII, CoII, R = Cym, a series of heterometallic polymers with metal cores {Cu2Fe}n (1), {Cu2Mn4Fe}n (2) {Ni2Mn4Fe}n (3), and {Co2Mn4Fe}n (4) were obtained under mild conditions. Compounds 1 and 2 showed antibacterial activity against a Mycobacterium smegmatis strain in vitro. Heterotrimetallic coordination polymers with metal core FeCu2, FeCu2Mn4, FeCo2Mn4, FeNi2Mn4 using functionalized cymantrene and ferrocene are synthesized and their antibacterial activity has been studied.

The antiproliferative and antibacterial effects of copper( ii ) complexes with the same ligand environment have been studied depending on the anion.

The unique palladium complexes [PdPhen((CF3)2pz)2] (1), [PdPhen(MeCF3pz)2] (2) and [Pd2Phen2(µ-dmpz)2(dmpz)(Hdmpz)](MeCOO)2H (3). have been obtained by interaction of [PdPhen(OOCMe)2] (Phen=1,10-phenanthroline, Me=methyl) with 3,5-bis(trifluoromethyl)pyrazole (3,5-(CF3)2pzH), 3-methyl-5-trifluoromethylpyrazole (3-Me-5-CF3pzH) and 3,5-dimethylpyrazole (Hdmpz), respectively. According to the X-ray data, in mononuclear pyrazolate complexes 1 and 2, the Pd (II) has a square planar environment of nitrogen atoms of phenanthroline and two monodentate-bound pyrazolate anions. Compound 3 is a binuclear pyrazolate-bridged complex, additionally stabilized by intramolecular hydrogen bonding of the terminal dmpz anion and Hdmpz.

The β-substituted porphyrinoids commonly used to form functional assembled systems in nature yet are still scarcely used in material chemistry probably due to the laborious synthesis of these compounds. In this work, β-octa[(4-diethoxyphosphoryl)phenyl]porphyrin (2HOPPP) and its metal (Zn(II), Cd(II), Cu(II), and Ni(II)) complexes were prepared in good yields. These highly soluble chromophores were characterized in solution using spectroscopic (NMR, UV-vis, fluorescence), electrochemical, and spectroelectrochemical methods. Attachment of the electron-deficient residue (ArP(O)(OEt)2) to the porphyrin macrocycle leads to easier reductions and harder oxidations of the macrocycle for all complexes studied as compared to corresponding meso-tetra[4-(diethoxyphosphoryl)phenyl]porphyrin derivatives reported previously. We demonstrated that the strong electron-deficient character of the MOPPP porphyrins results principally from the increase in the number of electron-withdrawing groups at the periphery of the tetrapyrrolic macrocycle. Electron-deficient porphyrins are highly required in supramolecular and material chemistry in part due to their ability to form supramolecular assemblies via the coordination of axial ligands to the central metal atom. According to single-crystal X-ray data, ZnOPPP forms in the crystalline phase dimers in which each of the two tetrapyrrolic macrocycles is connected through an unusual combination of hydrogen bonding of two phosphoryl groups and the water molecules axially coordinated to the zinc atom of the partner molecule. The involvement of water molecules in porphyrin binding allows for an increase of distance between two porphyrin mean N4 planes, up to 4.478 Å. The offset of phosphoryl groups attached to the macrocycle through a 1,4-phenylene spacer withdraws the whole porphyrin macrocycle of one molecule from spatial overlap with the macrocycle of a partner molecule and increases the Zn-Zn distance up to 10.372 Å. This still unknown type of porphyrin dimers allows one to get deeper insights into the organization of naturally occurring tetrapyrrolic macrocycles. ZnOPPP also forms a labile dimeric complex in 5.3 × 10-7-5.8 × 10-5 M chloroform solutions. In contrast, other complexes prepared in this work exist as monomeric species under these experimental conditions. The self-association constant of ZnOPPP has been determined by electronic absorption spectroscopy.

A series of 5,7-disubstituted 1,4-diazepinoporphyrazinato magnesium(II) and nickel(II) complexes, including two novel compounds, were obtained by metal-templated macrocyclization. A combination of X-ray diffraction, 1H NMR, UV-vis, and electrochemical analyses allowed us to study their tendency towards H-type dimerization and trace the influence of structural and solvation factors on dimer stability. Based on the physicochemical and theoretical DFT calculation data, it was found that the main binding forces between 6H-1,4-diazepinoporphyrazine decks in the dimers were efficient π-π donor-acceptor interactions induced by the interdeck C-H⋯N hydrogen bonds. Furthermore, the metal-ligand (Pz2- → M2+) electronic interactions have a key influence on the π-π stacking of the porphyrazine cores. It was shown that the displacement of the metal ion out of the macrocycle plane induced by coordinating agents can trigger the dissociation of the dimer, since the resulting enhancement of the donor-acceptor electronic interaction between the metal ion and the π-system of the ligand leads to a subsequent weakening of the π-π stacking of the porphyrazine cores. The TD-DFT calculations predicted the non-degeneracy of the HOMO-1 → LUMO and HOMO → LUMO+1 transitions in the 6H-1,4-diazepinoporphyrazine H-dimers, which explains the Q-band splitting in their UV-vis spectra.

It was shown that refluxing of europium(III) acetate hydrate with trifluoroacetic acid in a dioxane–acetonitrile mixture gives the polymer {[Eu(μ-OOCCF 3 ) 3 (OH 2 ) 2 ]} n ( I ) containing dioxane solvate molecules. The reaction of I with [phen(µ-OOC t Bu) 2 (OOC t Bu) 2 ] ( II ) (phen = 1,10-phenanthroline) in CH 2 Cl 2 at room temperature gives a precipitate, the recrystallization of which from acetonitrile affords an unusual trinuclear heterometallic heteroanionic phen 2 Zn 2 Eu(µ 3 -OH)(OOC t Bu) 4 (OOCCF 3 ) 2 complex ( III ). The structure of the products was established from X-ray diffraction data (CCDC no. 2235937–2235939). The optical properties of complex III were studied.

It has been shown that boiling aqueous europium(III) acetate with trifluoroacetic acid in a dioxane-acetonitrile mixture leads to the formation of a polymer {[Eu(μ-OOCCF3)3(OH2)2]}n (I) containing solvate dioxane molecules. The interaction of I in CH2Cl2 with [Phen2Zn2(µ-OOCBut)2(OOCBut)2] (II) at room temperature forms a precipitate, recrystallization of which from acetonitrile gives an unusual trinuclear heterometallic heteroanionic complex Phen2Zn2Eu(µ3-OH)(OOCBut)4(OOCCF3 )2 (III). The structure of the obtained compounds was established according to X-ray diffraction data (CCDC No. 2235937-2235939). The optical properties of complex III were studied.

The reactions of 3,5-bis(trifluoromethyl)pyrazole ((CF 3 ) 2 PzH) with the binuclear complex [Phen 2 Co 2 (μ-OH 2 )(μ-OOCMe) 2 (OOCMe) 2 ] were studied. The reaction in dichloromethane under mild conditions gave the complex [Co 2 (Phen) 2 (µ-H 2 O)(µ-OOCMe) 2 (OOCMe) 2 ]((CF 3 ) 2 PzH) 4 ( I ). Refluxing of I in ortho -xylene resulted in deprotonation of pyrazole giving two mononuclear complexes: pyrazolate [Co(Phen) 2 (H 2 O)(OOCMe)]((CF 3 ) 2 Pz) ( II ) and pyrazolate acetate [Co(Phen) 2 ((CF 3 ) 2 Pz) 2 ] ( III ). Compounds I – III were studied by X-ray diffraction (CCDC nos. 2159355–2159357), IR spectroscopy, and elemental analysis. The thermal behavior of I was investigated by TGA.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The Corey-Chaykovsky method was used for α,α-cyclopropanation of dehydroalanine in the form of chiral Ni(II) Schiff-base complexes. For generation of the Corey ylide, electrochemical and chemical deprotonation were tested. For sulphonium salts more easily reduced than the Michael acceptor, the direct electrochemical reduction of the salt in the presence of the dehydroalanine complex gives almost quantitative yield of the cyclopropanated amino acid derivative. For the salts reduced at more cathodic potentials than the Ni-Schiff-base complex and are not prone to rearrangements, electrochemical deprotonation followed by the addition of the complex gives significantly higher yield of the cyclopropanated complex then deprotonation with common bases. Notably, insertion of the substituent either in the sulphonium salt or at the double bond of the dehydroalanine complex yields formation of the cyclopropane derivatives with the opposite configurations of the β-stereocenter. The (R;R,cis)-isomer dominates in the former case whereas the (S;R,trans)-diastereomer is formed in the latter case. To shed light on the stereoselectivity observed, the activation free energies for four alternative ring-closure steps leading to four possible diastereomers were calculated using the DFT approach.

Ru(II) complexes with polypyridyl ligands play a central role in the development of photocatalytic organic reactions. This work is aimed at the structural modification of such complexes to increase their photocatalytic efficiency and adapt them for the preparation of reusable photocatalytic systems. Nine [Ru(phen)(bpy)2]2+-type complexes (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) (Ru-Pcat) bearing the P(O)(OEt)2 substituent attached to the phen core directly or through a 1,4-phenylene linker were synthesized and characterized by spectroscopic and electrochemical techniques. The coordination mode of phen ligands was confirmed by single crystal X-ray analysis. The (spectro)electrochemical data show that the first electron transfer in Ru-Pcat takes place on the phen ligand. The emission maxima and quantum yields are strongly affected by the substitution pattern, reaching the far-red region (697 nm) for Ru-3,8P2. The singlet oxygen quantum yields of Ru-Pcat were evaluated using the chemical trapping method. Finally, the photocatalytic performance of Ru-Pcat in the oxidation of sulfides with molecular oxygen was investigated. Both dialkyl and alkyl aryl sulfides were quantitatively transformed into sulfoxides under irradiation with a blue LED in the acetonitrile-water mixture (10 : 1) using a low loading of 0.005-0.05 mol% Ru(II) photocatalysts. To rationalize the effect of phosphonate substituents on the photocatalytic efficiency, comparative kinetic studies of (1) 4-nitrothioanisole oxidation proceeding predominantly via the electron transfer pathway and (2) oxidation of dibutyl sulfide wherein singlet oxygen serves as an oxidant have been performed. It was demonstrated that complexes with the P(O)(OEt)2 substituent at positions 4 and 7 outperform the benchmark photocatalyst Ru-(bpy)3 and the parent complex Ru-phen in the reactions proceeding through electron transfer (reductive quenching photocatalytic cycle). The TON in the oxidation of 4-methoxythioanisole was found to be as high as 1 000 000 that is, to our knowledge, the highest among previously reported photocatalysts. In contrast, upon separating the P(O)(OEt)2 group and the phen core with the 1,4-phenylene linker, singlet oxygen quantum yields significantly increase that favors reactions proceeding through energy transfer (the oxidation of dibutyl sulfide in our case). Thus, both series of Ru(II) complexes prepared in this work are promising for the improvement of known photocatalytic reactions and the development of new transformations.

An efficient strategy for the preparation of a novel series of benzothiadiazole-containing isoquinoline-bridged D-A compounds based on Cp*Rh(III)-catalyzed redox-neutral annulation of N-(pivaloyloxy)-benzamides with 4-ethynyl-7-(p-methoxyphenyl)-2,1,3-benzothiadiazole as a key step followed by the installation of donor units, such as diphenylamine, carbazole, and dihydrodibenzoazepine, by aromatization and Suzuki coupling reactions, has been developed. An initial photophysical, electrochemical and DFT investigations of the selected products have been performed.

The reaction of cymantrenates M[(OOС5CH4)Mn(CO)3]2(MeOH)4 (M = Zn, Co(II), Ni(II)) with pyrazole (HPz) results in replacement of labile methanol molecules by the heterocyclic ligand and gives mononuclear complexes Zn[(OOCC5H4)Mn(CO)3]2(HPz)2 (I), Ni[(OOCC5H4)Mn(CO)3]2(HPz)4 (II), and Co[(OOCC5H4)Mn(CO)3]2(HPz)4 (III). A similar reaction of cobalt cymantrenate with more basic and sterically bulky 3,5-dimethylpyrazole (HDmpz) gives the complex Co[(OOCC5H4)Mn(CO)3]2(HDmpz)2 (IV). Compounds I–IV were characterized by X-ray diffraction (CCDC nos. 2157671 (I), 2157672 (II), 2157669 (III), and 2157670 (IV)), IR spectroscopy, and elemental analysis.