(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.     

Synthesis and structures of photoactive rhenium carbonyl complexes derived from 2‐(pyridin‐2‐yl)‐1,3‐benzothiazole, 2‐(quinolin‐2‐yl)‐1,3‐benzothiazole and 1,10‐phenanthroline

Carbon monoxide (CO) has recently been identified as a gaseous signaling molecule that exerts various salutary effects in mammalian pathophysiology. Photoactive metal carbonyl complexes (photoCORMs) are ideal exogenous candidates for more controllable and site‐specific CO delivery compared to gaseous CO. Along this line, our group has been engaged for the past few years in developing group‐7‐based photoCORMs towards the efficient eradication of various malignant cells. Moreover, several such complexes can be tracked within cancerous cells by virtue of their luminescence. The inherent luminecscent nature of some photoCORMs and the change in emission wavelength upon CO release also provide a covenient means to track the entry of the prodrug and, in some cases, both the entry and CO release from the prodrug. In continuation of the research circumscribing the development of trackable photoCORMs and also to graft such molecules covalently to conventional delivery vehicles, we report herein the synthesis and structures of three rhenium carbonyl complexes, namely, fac‐tricarbonyl[2‐(pyridin‐2‐yl)‐1,3‐benzothiazole‐κ²N ,N ′](4‐vinylpyridine‐κN )rhenium(I) trifluoromethanesulfonate, [Re(C₇H₇N)(C₁₂H₈N₂S)(CO)₃](CF₃SO₃), ( 1 ), fac‐tricarbonyl[2‐(quinolin‐2‐yl)‐1,3‐benzothiazole‐κ²N ,N ′](4‐vinylpyridine‐κN )rhenium(I) trifluoromethanesulfonate, [Re(C₇H₇N)(C₁₆H₁₀N₂S)(CO)₃](CF₃SO₃), ( 2 ), and fac‐tricarbonyl[1,10‐phenanthroline‐κ²N ,N ′](4‐vinylpyridine‐κN )rhenium(I) trifluoromethanesulfonate, [Re(C₇H₇N)(C₁₂H₈N₂)(CO)₃](CF₃SO₃), ( 3 ). In all three complexes, the Re^I center resides in a distorted octahedral coordination environment. These complexes exhibit CO release upon exposure to low‐power UV light. The apparent CO release rates of the complexes have been measured to assess their comparative CO‐donating capacity. The three complexes are highly luminescent and this in turn provides a convenient way to track the entry of the prodrug molecules within biological targets.     

Solvent‐Free Synthesis of 2‐(Phenylamino)‐4‐(trifluoromethyl)‐1,6‐dihydropyrimidine Derivatives Catalyzed by Sulfamic Acid

A series of 2‐(phenylamino)‐4‐(trifluoromethyl)‐1,6‐dihydropyrimidine derivatives were synthesized efficienly via the reaction of aryl aldehyde, ethyl 4,4,4‐trifluoro‐3‐oxobutanoate and 1‐phenylguanidine carbonate catalyzed by sulfamic acid under solvent‐free conditions. This protocol has the advantages of mild condition, high yields and environmentally benign procedure.     

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.     

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.     

Antibacterial Activities and Nuclease Properties of Two New Ternary Copper(II) Complexes with 2‐(4′‐Thiazolyl)‐benzimidazole and 2,2′‐Bipyridine/1,10‐phenanthroline

Two new complexes: [Cu(TBZ)(bipy)Cl]Cl·H₂O ( 1 ) and [Cu(TBZ)(phen)Cl]Cl·H₂O ( 2 ) [TBZ=2‐(4′‐thiazolyl)‐ benzimidazole, phen=1,10‐phenanthroline and bipy=2,2′‐bipyridine] have been synthesized and characterized by elemental analysis, molar conductivity, IR, and UV‐vis methods. Complex 2 , structurally characterized by single‐crystal X‐ray crystallography, crystallizes in the monoclinic space group P2₁/c in a unit cell of a=0.85257(12) nm, b=2.5358(4) nm, c=1.15151(13) nm, β=118.721(8)°, V=2.183.2(5) nm³, Z=4, D_c=1.624 g·cm⁻³, µ=1.367 mm⁻¹. The complexes, free ligands and chloride copper(II) salt were each tested for their ability to inhibit the growth of two gram‐positive (B. subtilis and S. aureus) and two gram‐negative (Salmonella and E. coli) bacteria. The complexes showed good antibacterial activities against the microorganisms. The interaction between the complexes and calf thymus DNA in aqueous solution was investigated adopting electronic absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and cyclic voltammetry. Results suggest that the two complexes can bind to DNA by intercalative mode. In addition, the result of agarose gel electrophoresis suggested that the complexes can cleave the plasmid DNA at physiological pH and room temperature. Mechanistic studies with different inhibiting reagents reveal that hydroxyl radicals, and a singlet oxygen‐like copper‐oxo species are all involved in the DNA scission process mediated by the complexes.     

Crystallographic report: (2,9‐Dimethyl‐1,10‐phenanthroline)bis‐(N,N‐pyrrolidinedithiocarbamato)zinc(II) chloroform hemihydrate

The mononuclear structure of Zn(S₂C(N(CH₂)₂)₄)₂(2,9‐Me₂‐1,10‐phen) shows monodentate coordination by the dithiocarbamate ligands and a distorted tetrahedral geometry for zinc, defined by an N₂S₂ donor set, results. Copyright © 2003 John Wiley & Sons, Ltd.     

稀土3，4-呋喃二甲酸，1，10-二氮杂菲配合物的光物理性质

研究了稀土Ｇｄ３＋、Ｅｕ３＋、Ｔｂ３＋的３，４呋喃二甲酸，１，１０二氮杂菲（Ｐｈｅｎ）配合物的合成、红外光谱、紫外光谱及光物理性质。详细讨论了配合物的分子内能量传递过程。发现分子内能量传递效率依赖于稀土中心离子的共振发射能级与配体最低三重态能级之间的相对位置。     

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.     

Bis[μ‐1‐(1,10‐phenanthrolin‐2‐yl)‐2‐pyridone]bis{aqua[1‐(1,10‐phenanthrolin‐2‐yl)‐2‐pyridone]cadmium(II)} tetrakis(perchlorate)

In the title centrosymmetric binuclear complex, [Cd₂(C₁₇H₁₁N₃O)₄(H₂O)₂](ClO₄)₄, the Cd^II ion assumes a distorted octahedral geometry. There are π–π stacking interactions between the pyridine and 1,10‐phenanthroline ring systems of adjacent ligands at the same Cd^II centre. Intermolecular hydrogen bonds between the coordinated aqua ligand and the O atom of a keto group connect adjacent complex cations into extended chains. Hydrogen bonds also exist between the complex cations and the perchlorate anions. Compared with the fluorescence spectrum of the organic ligand, the complex displays strong fluorescent emission and an ipsochromic shift of the emission peaks, which may be attributed to the structural character.     

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.     

Fluorescent Dendritic Organogels Based on 2‐(2′‐Hydroxyphenyl)benzoxazole: Emission Enhancement and Multiple Stimuli‐Responsive Properties

A new highly efficient and versatile poly(benzyl ether) dendritic organogelator HPB‐G₁ with 2‐(2′‐hydroxyphenyl)benzoxazole (HPB) at the focal point has been designed and synthesized. HPB‐G₁ can form stable organogels toward various apolar and polar organic solvents. Further studies revealed that intermolecular multiple π–π stacking interactions are the main driving forces for the formation of the organogels. Notably, dendron HPB‐G₁ exhibited a significantly enhanced emission in the gel state in contrast to weak emission in solution. Most interestingly, these dendritic organogels exhibited multiple stimuli‐responsive behaviors upon exposure to environmental stimuli, including temperature, sonication, shear stress, and the presence of anions, metal cations, acids/bases, thus leading to reversible sol–gel phase transitions.     

Crystal structure,shape analysis and bioactivity of new LiI,NaI and MgII complexes with 1,10‐phenanthroline and 2‐(3,4‐dichlorophenyl)acetic acid

Reactions of 1,10‐phenanthroline (phen) and 2‐(3,4‐dichlorophenyl)acetic acid (dcaH) with M_n(CO₃) (M = Li^I, Na^I and Mg^II; n = 1 and 2) in MeOH yield the mononuclear lithium complex aqua[2‐(3,4‐dichlorophenyl)acetato‐κO](1,10‐phenanthroline‐κ²N,N′)lithium(I), [Li(C₈H₅Cl₂O₂)(C₁₂H₈N₂)(H₂O)] or [Li(dca)(phen)(H₂O)] ( 1 ), the dinuclear sodium complex di‐μ‐aqua‐bis{[2‐(3,4‐dichlorophenyl)acetato‐κO](1,10‐phenanthroline‐κ²N,N′)sodium(I)}, [Na₂(C₈H₅Cl₂O₂)₂(C₁₂H₈N₂)₂(H₂O)₂] or [Na₂(dca)₂(phen)₂(H₂O)₂] ( 2 ), and the one‐dimensional chain magnesium complex catena‐poly[[[diaqua(1,10‐phenanthroline‐κ²N,N′)magnesium]‐μ‐2‐(3,4‐dichlorophenyl)acetato‐κ²O:O′] 2‐(3,4‐dichlorophenyl)acetate monohydrate], {[Mg(C₈H₅Cl₂O₂)(C₁₂H₈N₂)(H₂O)₂](C₈H₅Cl₂O₂)·H₂O}_n or {[Mg(dca)(phen)(H₂O)₂](dca)·H₂O}_n ( 3 ). In these complexes, phen binds via an N,N′‐chelate pocket, while the deprotonated dca^? ligands coordinate either in a monodentate (in 1 and 2 ) or bidentate (in 3 ) fashion. The remaining coordination sites around the metal ions are occupied by water molecules in all three complexes. Complex 1 crystallizes in the triclinic space group P with one molecule in the asymmetric unit. The Li⁺ ion adopts a four‐coordinated distorted seesaw geometry comprising an [N₂O₂] donor set. Complex 2 crystallizes in the triclinic space group P with half a molecule in the asymmetric unit, in which the Na⁺ ion adopts a five‐coordinated distorted spherical square‐pyramidal geometry, with an [N₂O₃] donor set. Complex 3 crystallizes in the orthorhombic space group P2₁2₁2₁, with one Mg²⁺ ion, one phen ligand, two dca^? ligands and three water molecules in the asymmetric unit. Both dcaH ligands are deprotonated, however, one dca^? anion is not coordinated, whereas the second dca^? anion coordinates in a bidentate fashion bridging two Mg²⁺ ions, resulting in a one‐dimensional chain structure for 3 . The Mg²⁺ ion adopts a distorted octahedral geometry, with an [N₂O₄] donor set. Complexes 1 – 3 were evaluated against urease and α‐glucosidase enzymes for their inhibition potential and were found to be inactive.     

A molybdenum complex with 4,7‐­diphenyl‐1,10‐phenanthroline

In the title compound, tetra­carbonyl­(4,7‐di­phenyl‐1,10‐phen­an­throline‐N,N′)­molyb­denum(0), [Mo(C₂₄H₁₆N₂)(CO)₄], the Mo‐atom coordination is distorted octahedral, with two CO groups cis to each other, but each trans to an N atom of the 4,7‐di­phenyl‐1,10‐phenanthroline (dpphen) ligand, and with the other two CO groups trans to each other and on the axis position. The complex has better solubility than [Mo(phen)(CO)₄], where phen is 1,10‐phenanthroline.     

Hydrogen‐bonding and π–π stacking interactions in aquachloridobis(1,10‐phenanthroline)cobalt(II) chloride dichloridobis(1,10‐phenanthroline)cobalt(II) hexahydrate

The title compound, [CoCl(C₁₂H₈N₂)₂(H₂O)]Cl·[CoCl₂(C₁₂H₈N₂)₂]·6H₂O, is the first example of a new 1:1 cocrystal of the octahedral [CoCl₂(phen)₂] and [CoCl(phen)₂(H₂O)]⁺·Cl⁻ complexes (phen is 1,10‐phenanthroline). The latter form heterochiral dimers held by strong π–π stacking interactions via their phenathroline ligands, which confirms that π stacking is an important and reliable synthon in supramolecular design. In addition, the crystal structure is networked by H₂O...H₂O, H₂O...Cl⁻ and H₂O...Cl hydrogen bonds, which interconnect the different units of the cobalt complexes.     

Tris(1,10‐phenanthroline)sodium 2,4,6‐trimercapto‐1,3,5‐triazin‐1‐ide

The title compound, [Na(C₁₂H₈N₂)₃](C₃H₂N₃S₃), contains an Na⁺ centre which is ionicly bonded to three 1,10‐phenanthroline (phen) ligands and one tri­thio­cyanurate(1−) (ttcH₂) anion. In the crystal structure, the anions are linked via hydrogen bonds to form linear chains. The S and H atoms of the ttcH₂ anion participate in intermolecular N—H⋯S hydrogen bonding, with N⋯S distances of 3.298 (2) and 3.336 (2) Å. The phen ligands are almost parallel, with dihedral angles of 3.92 (5), 11.75 (5) and 15.45 (5)°; moreover, they are nearly perpendicular to the ttcH₂ chains, with angles of 81.94 (7), 85.86 (7) and 85.96 (7)°.     

Synthesis of 4‐(Phenylamino)quinazoline‐2(1H)‐selones and Diselenides from Isoselenocyanates: Dimroth Rearrangement of an Intermediate

The reaction of anthranilonitriles 8 with phenyl isoselenocyanates ( 1a ) in dry pyridine under reflux gave 4‐(phenylamino)quinazoline‐2(1H)‐selones 9 (Scheme 2). They are easily oxidized and converted to diselenides of type 11 . The analogous reaction of 8a with phenyl isothiocyanate ( 1b ) yielded the quinazoline‐2(1H)‐thione 10 (Scheme 2). A reaction mechanism via a Dimroth rearrangement of the primarily formed intermediate is presented in Scheme 3. The molecular structures of 10 and 11a have been established by X‐ray crystallography. Unexpectedly, no selone or diselenide was obtained in the case of the reaction with 3‐aminobenzo[b]furan‐2‐carbonitrile ( 14 ). The only product isolated was the selenide 16 (Scheme 4), the structure of which has been established by X‐ray crystallography.     

Facile acidic hydrolysis and displacement reactions of 2‐chloro‐and 2,9‐dichloro‐1,10‐phenanthroline

Treatment of 2‐chloro‐ or 2,9‐dichloro‐1,10‐phenanthroline with aqueous HBr or aqueous H₂SO₄ at 120°C yielded 1,10‐phenanthroline‐2(1H)‐one or 1,10‐dihydro‐1,10‐phenanthroline‐2,9‐dione, respectively. The hydrolysis of 2,9‐dichloro‐1,10‐phenanthroline with 37% aqueous HC1 led to the half hydrolyzed amide and the bis‐amide. Under comparable reactions conditions, using aqueous HBr, H₂SO₄ or HC1, 2‐chloropyridine was found to be hydrolytically stable. On the other hand, 2‐chloro‐ or 2,9‐dichloro‐1,10‐phenanthroline on heating with 57% aqueous HI afforded the HI salts of 2‐iodo‐ or 2,9‐diiodo‐1,10‐phenanthroline, which could be isolated. These salts on treatment with aqueous ammonium hydroxide led to good yields of 2‐iodo‐ and 2, 9‐diiodo‐1,10‐phenanthroline, respectively. Treatment of 2‐chloropyridine with 57% aqueous HI under similar reaction conditions led to 2‐iodopyridine in a 10% conversion.