An unusual eight‐coordinated copper complex: bis­(4,7‐diphenyl‐1,10‐phenanthroline)dinitratocopper(II)

In the title monomer, [Cu(NO₃)₂(C₂₄H₁₆N₂)₂], the copper(II) cation is eight‐coordinate within an octa­hedral‐like polyhedron. The coordination polyhedron is formed by two chelating diphenyl­phenanthroline groups that define the highly distorted CuN₄ equatorial plane and two weakly bound bidentate (chelating) nitrate groups in the apical or axial positions. The complex crystallizes in the monoclinic space group C2/c; a twofold axis passes through the copper(II) cation and bis­ects the two nitrate ligands. This gives the mol­ecule C₂ point‐group symmetry, rendering only half of the mol­ecule independent.     

A novel copper(II) complex with 1,10‐phenanthroline and ciprofloxacin

The X‐ray structure analysis of the title compound, chloro[1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐4‐ium‐1‐yl)‐3‐quinolinecarboxylate‐κ²O³,O⁴](1,10‐phenanthroline‐κ²N,N′)copper chloride dihydrate, [CuCl(C₁₇H₁₈FN₃O₃)(C₁₂H₈N₂)]Cl·2H₂O or [CuCl(cfH)(phen)]Cl·2H₂O, where cfH is 1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐4‐ium‐1‐yl)‐3‐quinolinecarboxylate and phen is 1,10‐phenanthroline, shows that the geometry around the Cu ion is a slightly distorted square pyramid. Two O atoms of the carbonyl and carboxyl groups of ciprofloxacin and two N atoms of 1,10‐phenanthroline are coordinated to the metal centre in the equatorial plane, and a Cl⁻ ion is coordinated at the apical position. Extensive intermolecular hydrogen bonding produces a supramolecular structure that consists of alternating six‐ and 12‐membered rings.     

Electrochemiluminescence Based on Solid State Tri(4,7‐diphenyl‐1,10‐phenanthroline) Ruthenium(II) Ditetrakis(4‐chlorophenyl) Borate Immobilized on Carbon Fibers

A simple method for immobilization of tri(4,7‐diphenyl‐1,10‐phenanthroline) ruthenium(II) ditetrakis(4‐chlorophenyl) borate ([Ru(dpp)₃][(4‐Clph)₄B]₂) on carbon fiber electrodes was developed. Excellent electrochemical activity and electrochemiluminescence (ECL) signal of the coated carbon fiber electrodes were observed using oxalate as the co‐reactant. In addition, the effects of pH, scan rate, nitrogen and oxygen on ECL intensity were also studied. To demonstrate the reliability, the coated carbon fiber electrodes were used as ECL detectors and very low concentration of phenol was detectable (5.0×10^?8 M).     

(4‐Bromo‐2‐formyl­phenolato)­perchlorato­(1,10‐phenanthroline)­copper(II)

In the title copper(II) compound, [Cu(C₇H₄BrO₂)(ClO₄)(C₁₂H₈N₂)], the Cu atom is five‐coordinated in a distorted square‐pyramidal geometry by the N‐ and O‐donors of 4‐bromo‐2‐formyl­phenolate, 1,10‐phenanthroline and perchlorate. Pairs of complexes are linked together by Cu⋯O(phenolate) and π–π stacking inter­actions between 4‐bromo‐2‐formyl­phenolate and 1,10‐phenanthroline. Along the crystallographic a axis, the dimers are linked by hydrogen bonds between a perchlorate O atom and a 4‐bromo‐2‐formyl­phenolate H atom, and by further π–π stacking inter­actions. Hydrogen bonding between the Br atom and a 1,10‐phenanthroline H atom takes place between the stacks of dimers.     

A new two‐dimensional cadmium metal–organic framework: poly[bis(4,7‐diphenyl‐1,10‐phenanthroline)(μ3‐5‐nitroisophthalato)cadmium(II)]

In the title cadmium metal–organic framework complex, [Cd(C₈H₃NO₆)(C₂₄H₁₆N₂)]_n or [Cd(NIPH)(dpphen)] (NIPH is nitroisophthalate and dpphen is 4,7‐diphenyl‐1,10‐phenanthroline), the unique Cd^II cation in a general position is coordinated by four carboxy O atoms from three symmetry‐related NIPH anions and two N atoms from a dpphen ligand. The Cd^II cations are bridged by pairs of NIPH anions to generate a dinuclear molecular building block, [Cd₂N₄(CO₂R)₄], with a Cd...Cd separation of 4.0936 (10) Å. Each such building block is connected to four adjacent dinuclear building blocks by NIPH anions, resulting in a two‐dimensional layer framework in the bc plane. The dpphen ligands occupy the space between these layers and are linked by π–π interactions, with a separation of 3.4541 (6) Å between the central aromatic rings of inversion‐related dpphen ligands. The thermogravimetric and photoluminescent properties of the complex have also been investigated.     

Solid Contact Nitrate Ion‐selective Electrode Based on Cobalt(II) Complex with 4,7‐Diphenyl‐1,10‐phenanthroline

Nitrates are a group of compounds widely distributed in the natural environment with many applications in various industries. Due to their ambiguous impact on the human body and suspicions of their carcinogenic activity, they have been very popular for decades and are the subject of research by many scientists in the field of medicine, biology and chemistry. Due to the need to monitor their content in environmental and food samples, various methods for their determination are developed. This paper proposes the use of a nitrate ion‐sensitive ion selective electrode with a membrane containing as the active ingredient a new cobalt(II) complex with 4,7‐diphenyl‐1,10‐phenanthroline (Bphen) of the formula Co(Bphen)₂(NO₃)₂(H₂O)₂. The obtained sensor showed the theoretical slope of the characteristic curve, a wide measuring range, as well as short response time and very good potential stability. It was successfully used for the determination of nitrates in real samples: in mineral water, tap water and river water from eastern Poland.     

A supramolecular cadmium(II) complex: (1,10‐phenanthroline)[tris(2‐amino­ethyl)­amine]­cadmium(II) dinitrate hydrate

Colourless prismatic crystals of the title compound, [Cd(tren)(phen)](NO₃)₂·H₂O [phen = 1,10‐phen­an­thro­line, C₁₂H₈N₂; tren = tris(2‐amino­ethyl)­amine, C₆H₁₈N₄], form from an aqueous solution of equivalent amounts of Cd(NO₃)₂, tren and phen. Infinite one‐dimensional polymeric zigzag motifs, constructed via alternating hydrogen‐bonding and π–π interactions, are further mediated by nitrate–amine hydrogen bonds to create three‐dimensional networks.     

A mixed bridged trinuclear copper(II)–1,10‐phenanthroline complex with a linear structure

The title compound, diaqua‐1κO,3κO‐di‐μ‐hydroxido‐1:2κ²O:O,2:3κ²O:O‐di‐μ‐methacrylato‐1:2κ²O:O′,2:3κ²O:O′‐bis(1,10‐phenanthroline)‐1κ²N,N′;3κ²N,N′‐tricopper(II) dinitrate dihydrate, [Cu₃(C₄H₅O₂)₂(OH)₂(C₁₂H₈N₂)₂(H₂O)₂](NO₃)₂·2H₂O, has the central Cu atom on an inversion centre. The three Cu^II atoms are in a linear arrangement linked by methacrylate and hydroxide groups. The coordination environments of the Cu^II ions are five‐coordinated distorted square‐pyramidal for the outer Cu atoms and four‐coordinated square‐planar for the central Cu atom. All nitrate ions, hydroxide groups and water molecules are linked by hydrogen bonds, forming a linear structure. The complex exhibits ferromagnetic exchange coupling, which is helpful in elucidating magnetic interactions between copper ions and other metallic ions in heteronuclear complexes.     

Crystallographic report: Bis(O‐methoxyethyldithiocarbonato)(4,7‐dimethyl‐1,10‐phenanthroline)cadmium(II)

The structure of mononuclear Cd(S₂COCH₂CH₂OCH₃)₂(4,7‐Me₂phen) shows an N₂S₄ donor set about cadmium that defines a coordination geometry intermediate between octahedral and trigonal prismatic. Copyright © 2003 John Wiley & Sons, Ltd.     

Bis(μ‐2‐sulfonatobenzoato)bis[(1,10‐phenanthroline)­lead(II)] dihydrate

In the title centrosymmetric dimer, [Pb₂(sbc)₂(phen)₂]·2H₂O [sbc is the 2‐sulfonatobenzoate dianion (C₇H₄O₅S) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], each Pb^II ion is six‐coordinated by four O atoms, viz. carboxyl­ate and sulfonate O atoms from two sbc anions, and two N atoms from a 1,10‐phenanthroline ligand. One 1,10‐phenanthroline ligand and the carboxyl­ate group of one sbc ligand are chelated to each Pb^II cation, and the sulfonate group of the other sbc unit is monodentate. One O atom of the chelated carboxyl­ate group also bridges to the other Pb^II cation, so that each pair of Pb^II ions is bridged by two sbc anions and has the same coordination environment, forming a dinuclear ring. Each pair of Pb^II ions is thus connected by two different kinds of bridges, namely a carboxyl­ate short bridge and a carboxyl­ate–sulfonate long bridge. There is also a special position of site symmetry at the centre of the two Pb^II cations.     

Bis(1,10‐phenanthroline)(thio­sulfato)­manganese(II) methanol solvate and catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phenanthroline)­manganese(II)]‐μ‐thio­sulfato]

The structure of bis(1,10‐phenanthroline‐κ²N,N′)(thio­sulfato‐κ²O:S)­manganese(II) methanol solvate, [Mn(S₂O₃)(C₁₂H₈N₂)₂]·CH₃OH, is made up of Mn²⁺ centers coordinated to two bidentate phenanthroline (phen) groups and an S,O‐chelating thio­sulfate anion, forming monomeric entities. The structure of catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phen­anthro­line‐κ²N,N′)­manganese(II)]‐μ‐thio­sulfato‐κ²O:S], [Mn(S₂O₃)(C₁₄H₁₂N₂)(H₂O)₂]_n, is polymeric, consisting of Mn(dmph)(H₂O)₂ units (dmph is 2,9‐di­methyl‐1,10‐phenanthroline) linked by thio­sulfate anions acting in an S,O‐chelating manner.     

Crystallographic report: (4,7‐Diphenyl‐1,10‐phenanthroline) bis(pyrrolinedithiocarbamato)zinc(II) chloroform solvate

The mononuclear structure of Zn(S₂CN(CH₂)₄)₂(4,7‐Ph₂‐1,10‐phenanthroline) shows the zinc atom in each of the two independent molecules comprising the asymmetric unit to exist in a distorted octahedral geometry defined by an N₂S₄ donor set. Copyright © 2003 John Wiley & Sons, Ltd.     

Dimeric hexakis(4‐methyl­benzoato)­bis(1,10‐phenanthroline)didyspros­ium(III)

The title compound, [Dy₂(C₈H₇O₂)₆(C₁₂H₈N₂)₂], forms binuclear complexes, viz. di‐μ‐4‐methyl­benzoato‐κ⁴O:O′‐bis[bis(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)] tetra‐μ‐4‐methyl­benzoato‐κ⁸O:O′‐bis[(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)]. There are two independent binuclear com­plexes in the asymmetric unit, both of which are centrosymmetric. In one, the Dy^III ions are linked by two bridging 4‐­methyl­benzoate groups, while in the other, the Dy^III ions are linked by four bridging 4‐methyl­benzoate groups. The remaining 4‐methyl­benzoate groups and 1,10‐phenanthroline units coordinate to just one metal ion in bidentate modes.     

Synthesis of some novel derivatives of 1,10‐phenanthroline

The synthesis is described of a set of new N‐heterocyclic compounds which are derivatives of 1,10‐phenanthroline. The compounds are designed to be general purpose chelating agents which could function as tri‐, tetra‐ or hexadentate ligands with transition metal ions. Fused‐ring molecular components have been included in the design of the compounds so that they may function as binding agents to DNA through intercalation. This includes the synthesis of substituted derivatives of pyrazino[2,3‐f][1,10]phenanthroline and dipyrido[3,2‐a:2′3′‐c]phenazine.     

Synthesis,characterization and biological properties of mixed ligand complexes of cobalt(II/III) valproate with 2,9‐dimethyl‐1,10‐phenanthroline and 1,10‐phenanthroline

The synthesis of mononuclear cobalt(II/III) complexes with two different ligands (complex 2: [Co(valp)₂(2,9‐dmp)] and complex 3: [Co(valp)₂(H₂O)(1,10‐phen)]) was investigated and the characterization of both complexes was achieved using IR, UV–Vis, and single crystal X‐ray diffraction. Using single crystal X‐ray diffraction, the crystal structure of each of the complexes was determined. Additionally, the biological activity of these complexes was studied in five gram‐positive and four gram‐negative bacterial strains. Whereas in all gram‐negative bacteria tested, cobalt valproate complexes did not show any anti‐bacterial activity, both complexes had effects on gram positive bacteria. Complex 2 demonstrated good anti‐bacterial activity against all gram‐positive bacteria with inhibition zone diameter (IZD) ranging between 15–28 mm. Complex 3 exhibited low inhibition activity against all gram‐positive bacteria except E. faecalis with IZD ranging between 11.3–13.7 mm. Moreover, as an indication of its uses as industrial catalyst, the rate of bis(p‐nitrophenyl) phosphate (BNPP) hydrolysis when catalyzed by these complexes was measured at different temperatures, concentrations and pH. Complex 2 proved to be a better catalyst to induce the hydrolysis of BNPP.     

An efficient microwave‐assisted synthesis furo[3,4‐b]‐[4,7] phenanthroline and indeno[2,1‐b][4,7]phenanthroline derivatives in water

A series of furo[3,4‐b][4,7]phenanthroline and indeno[2,1‐b][4,7]phenanthroline derivatives were synthesized via a three‐component reaction of aromatic aldehydes, 6‐aminoquinoline and either tetronic acid or 1,3‐indanedione in water, under microwave irradiation without use of any catalyst. This green procedure offers several advantages including operational simplicity, clean reaction, and increased safety for small‐scale high‐speed synthesis.     

Aqua(nitrilo­triacetato)­(1,10‐phenanthroline)iron(III) monohydrate: a seven‐coordinate iron(III) complex

Reaction of 1,10‐phenanthroline (phen) with iron trichloride in the presence of sodium nitrilo­tri­acetate (NTA) resulted in the formation of red crystals of the title complex, [Fe(C₆H₆NO₆)(C₁₂H₈N₂)(H₂O)]·H₂O. The Fe atom has a distorted capped trigonal prismatic coordination comprised of one tetradentate NTA, one bidentate phen molecule and a water mol­ecule. Intermolecular O—H?O hydrogen bonds link the mol­ecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the solvent water mol­ecule, leading to an infinite ladder packing mode.     

A two‐dimensional CdII coordination polymer with 2,2′‐(disulfanediyl)dibenzoate and 1,10‐phenanthroline ligands

In poly[[μ₃‐2,2′‐(disulfanediyl)dibenzoato‐κ⁵O:O,O′:O′′,O′′′](1,10‐phenanthroline‐κ²N,N′)cadmium(II)], [Cd(C₁₄H₈O₄S₂)(C₁₂H₈N₂)]_n, the asymmetric unit contains one Cd^II cation, one 2,2′‐(disulfanediyl)dibenzoate anion (denoted dtdb²⁻) and one 1,10‐phenanthroline ligand (denoted phen). Each Cd^II centre is seven‐coordinated by five O atoms of bridging/chelating carboxylate groups from three dtdb²⁻ ligands and by two N atoms from one phen ligand, forming a distorted pentagonal–bipyramidal geometry. The Cd^II cations are bridged by dtdb²⁻ anions to give a two‐dimensional (4,4) layer. The layers are stacked to generate a three‐dimensional supramolecular architecture via a combination of aromatic C—H...π and π–π interactions. The thermogravimetric and luminescence properties of this compound were also investigated.     

Photophysical Properties of Fluorescent 2‐(Phenylamino)‐1,10‐phenanthroline Derivatives†

The present study details the experimental and theoretical characterization of the photophysical properties of 14 examples of 2‐(phenylamino)‐1,10‐phenanthrolines ( 1 ). The absorption spectra of 1 are substituent‐dependent but in a general manner present absorption bands at wavelengths of ~230; ~300; ~335 and a shoulder at ~380 nm. Electron‐donating groups (EDG) and electron‐withdrawing groups (EWG), respectively, result in bathochromic and hypsochromic shifts. Compounds 1 are highly luminescent, in contrast to phenanthroline, and emit in the region between 350 and 500 nm with substituent‐dependent λ_max emission. The emission spectra show a redshift for EDG (4‐OMe 62 nm; 4‐Me 19 nm) and a blueshift for EWG (4‐CN 41 nm; 4‐CF₃ 38 nm) relative to the emission of the unsubstituted parent compound 1a . Plotting the ${\mathbf{\lambda }}_{\mathbf{max}}^{\mathbf{\text{EM}}}$ against Hammett σ+ constants gave an excellent linear correlation demonstrating the electron‐deficient nature of the excited state and how the substituents (de)stabilize S₁. Theoretical calculations revealed a HOMO‐LUMO π‐π* electronic transition to S₁ which in combination with difference (S₁–S₀) in electron density maps revealed charge‐transfer character. Strongly electron‐withdrawing substituents switch off the charge transfer to give rise to a local excitation.     

2,2,4,4‐Tetramethyl‐1,5‐diphenyl‐6,7,8‐trioxa‐3‐thiabicyclo[3.2.1]­octane

The structure of the title ozonide, C₂₀H₂₂O₃S, produced without the use of ozone, has been defined at 123 (1) K. In the triclinic crystal, the mol­ecule has symmetry close to C_s, and its ozonide and 1,4‐oxa­thiane rings have envelope and chair conformations, respectively. The ozonide unit has an O—O bond length of 1.4721 (12) Å and a C—O—O—C torsion angle of ?1.45 (12)°.