Iron(II) PARACEST MRI contrast agents

The first examples of Fe(II) PARACEST magnetic resonance contrast agents are reported (PARACEST = paramagnetic chemical exchange saturation transfer). The iron(II) complexes contain a macrocyclic ligand, either 1,4,7-tris(carbamoylmethyl)-1,4,7-triazacyclononane (L1) or 1,4,7-tris[(5-amino-6-methyl-2-pyridyl)methyl]-1,4,7-triazacyclononane (L2). The macrocycles bind Fe(II) in aqueous solution with formation constants of log K = 13.5 and 19.2, respectively, and maintain the Fe(II) state in the presence of air. These complexes each contain six exchangeable protons for CEST which are amide protons in [Fe(L1)](2+) or amino protons in [Fe(L2)](2+). The CEST peak for the [Fe(L1)](2+) amide protons is at 69 ppm downfield of the bulk water resonance whereas the CEST peak for the [Fe(L2)](2+) amine protons is at 6 ppm downfield of bulk water. CEST imaging using a MRI scanner shows that the CEST effect can be observed in solutions containing low millimolar concentrations of complex at neutral pH, 100 mM NaCl, 20 mM buffer at 25 °C or 37 °C.     

Highly luminescent, visible-emitting lanthanide macrocyclic chelates stable in water and derived from the cyclen framework

Two new tetraazamacrocyclic ligands are designed with the aim of sensitizing the luminescence of Tb(III) and Eu(III) ions in water: L5 [1,4,7,10-tetrakis[N-(phenacyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane] and L6 [1,4,7,10-tetrakis[N-(4-phenylphenacyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane]. These ligands react with lanthanide trifluoromethanesulfonates to yield stable 1:1 complexes in water (log K = 12.89 +/- 0.15 for EuL5). X-ray diffraction on [Tb(L5)(H(2)O)](CF(3)SO(3))(3) (P1 macro, a = 13.308(3) A, b = 14.338(3) A, c = 16.130(3) A, alpha = 101.37(3) degrees, beta = 96.16(3) degrees, gamma = 98.60(3) degrees ) shows the Tb(III) ion lying on a C(4) axis and being 9-coordinate, with one water molecule bound in its inner coordination sphere. The absolute quantum yields are determined in aerated water for the complexes formed with ions used in fluoroimmunoassays (Ln = Sm, Eu, Tb, and Dy). Large values are found for [Tb(H(2)O)(L5)](3+) and [Eu(H(2)O)(L6)](3+), in line with the molecular design of the receptors: 23.1% and 24.7%, respectively. The intense luminescence of these ions results from efficient intersystem crossing and L --> Ln energy transfer processes, as well as from a suitable shielding of the emitting ions from radiationless deactivation.     

Solvent dependent conformational isomerism and ligand oxidation of novel Ru(II) cyclen complexes

The synthesis of cis-[Ru(II)(cyclen)(L)(x)](n+) (cyclen = 1,4,7,10-tetraazacyclododecane and L = 2,2'-bipyridine (bpy), phenanthroline (phen) or 4-cyanopyridinium (4-NCpyH(+))) is reported. The freshly prepared complexes are stable in aprotic solvents and cyclen undergoes oxidative dehydrogenation reaction at high pH. These compounds also present solvent dependent conformational isomerization.     

Synthesis and characterization of water-operative cationic and anionic metal-ion activated molecular receptors for aromatic anions

Two new, octadentate, water-soluble, macrocyclic ligands, 1,4,7,10-tetrakis((2S)-(-)-2-hydroxy-3-[3'-(N,N,N-trimethylammonium)-phenoxy]-propyl)-1,4,7,10-tetraazacyclododecane tetratriflate, ((S)-tmappc12 triflate, L1 triflate) and 1,4,7,10-tetrakis((2S)-(-)-2-hydroxy-3-[2'-sulfo-4'-methylphenoxy]-propyl)-1,4,7,10-tetraazacyclododecane, ((S)-sthmppc12, L2H4) have been prepared with a view to using them to study anion sequestration in aqueous solution. Their pKa and metal-ion binding constant values with a range of alkaline earth, transition, and post-transition metals are reported. The eight-coordinate, water-soluble Cd(II) complexes of (L1)4+ and (L2)4-, [CdL1](CF3SO3)6 and (NH4)2-[CdL2], the former cationic and the latter anionic, have both been shown to be capable of acting as anion receptors in aqueous solution. The binding constant values (log(K/M-1) given in parentheses) for binding by the cationic receptor to a range of aromatic anions in water are p-nitrophenolate (1.7), p-formylphenolate (2.1), p-nitrobenzoate (3.0), p-aminobenzoate (4.5), p-dimethylaminobenzoate (>4.5), D- and L-tryptophanate (1.6, 2.2), phenoxyacetate (2.1), and acetate (2.3). With the anionic receptor, nonzero binding constants were only measurable for p-nitrobenzoate (approximately 0.4), p-aminobenzoate (2.0), and p-dimethylaminobenzoate (1.8). By reference to the X-ray determined structures of related, but water-insoluble inclusion complexes, anion retention is thought to occur within a hydrophobic cavity, with four convergent hydroxy groups at its base, which develops in (L1)4+ and (L2)4- through the juxtapositioning of aromatic rings that occurs as a consequence of octadentate coordination.     

Aminoacid N-substituted 1,4,7-triazacyclononane and 1,4,7,10-tetraazacyclododecane Zn2+, Cd2+ and Cu2+ complexes. A preparative, potentiometric titration and NMR spectroscopic study

The pK(a)s and Zn2+, Cd2+ and Cu2+ complexation constants (K) for 1,4,7-tris[(2'S)-acetamido-2'-(methyl-3'-phenylpropionate)]-1,4,7-triazacyclononane, 1, 1,4,7-tris[(2'S)-acetamido-2'-(1'-carboxy-3'-phenylpropane)]-1,4,7-triazacyclononane, H(3)2, 1,4,7-tris[(2'S)-acetamido-2'-(methyl-3'-(1H-3-indolyl)propionate)]-1,4,7-triazacyclononane, 3, and 1,4,7,10-tetrakis[(2'S)-acetamido-2'-(methyl-3'-phenylpropionate)]-1,4,7,10-tetraazacyclododecane, 4, 1,4,7,10-tetrakis[(2'S)-acetamido-2'-(1'-carboxy-3'-phenylpropane)]-1,4,7,10-tetraazacyclododecane, H(4)5, in 20 : 80 v/v water-methanol solution are reported. The pK(a)s within the potentiometric detection range for H(3)1(3+) = 8.69 and 3.59, for H(6)2(3+) = 9.06, 6.13, 4.93 and 4.52, H(3)3(3+) = 8.79 and 3.67, H(4)4(4+) = 8.50, 5.62 and 3.77 and for H(8)5(4+) = 9.89, 7.06, 5.53, 5.46, 4.44 and 4.26 where each tertiary amine nitrogen is protonated. The complexes of 1: [Zn(1)]2+(9.00), [Cd(1)]2+ (6.49), [Cd(H1)]3+ (4.54) and [Cu(1)]2+ (10.01) are characterized by the log(K/dm3 mol(-1)) values shown in parentheses. Analogous complexes are formed by 3 and 4: [Zn(3)]2+ (10.19), [Cd(3)]2+ (8.54), [Cu(3)]2+ (10.77), [Zn(4)]2+ (11.41) [Cd(4)]2+ (9.16), [Cd(H4)]3+ (6.16) and [Cu(4)]2+ (11.71). The tricarboxylic acid H(3)2 generates a greater variety of complexes as exemplified by: [Zn(2)-] (10.68) [Zn(H2)] (6.60) [Zn(H(2)2)+] (5.15), [Cd(2)](-) (4.99), [Cd(H2)] (4.64), [Cd(H2(2))]+ (3.99), [Cd(H(3)2)]2+ (3.55), [Cu(2)](-) (12.55) [Cu(H2)] (7.66), [Cu(H(2)2)]+ (5.54) and [Cu(2)2](4-) (3.23). The complexes of H(4)5 were insufficiently soluble to study in this way. The 1H and 13C NMR spectra of the ligands are consistent with formation of a predominant Zn2+ and Cd2+ Delta or Lambda diastereomer. The preparations of the new pendant arm macrocycles H(3)2, 3, 4 and H(4)5 are reported.     

Homo- and heteropolynuclear Ni2+ and Cu2+ complexes of polytopic ligands, consisting of a tren unit substituted with three 12-membered tetraazamacrocycles

Two new polytopic ligands L1 and L2 have been synthesized. They consist of a central tren unit to which three 1,4,7,10-tetraazacyclododecane rings are attached via an ethylene and a trimethylene bridge, respectively. The complexation properties of L1 and L2 towards Cu(2+) and Ni(2+) were studied by potentiometric pH titration, UV-Vis, EPR spectroscopy and kinetic techniques. As a comparison, the Cu(2+) and Ni(2+) complexes with L3 (1-(N-methyl-2-aminoethyl-1,4,7,10-tetraazacyclododecane)) were also investigated. The crystal structures of [CuL3H(H(2)O)](ClO(4))(3) and [NiL3Cl](ClO(4)) were solved and show that the side chain in its protonated form is not involved in coordination, whereas deprotonated it binds to the metal ion. The thermodynamically stable 3:1 complexes of L1 or L2 have a metal ion in the three macrocyclic units. However, when three equivalents of Cu(2+) are added to L1 or L2 the metal ion first binds to the tren unit and only then to the macrocycles. The kinetics of the different steps of complexation have been studied and a mechanism is proposed.     

Complexing mechanism of the lanthanide cations Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota)-characterization of three successive complexing phases: study of the thermodynamic and structural properties of the complexes by potentiometry, luminescence spectroscopy, and EXAFS

Complexation of the lanthanides Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota) has been studied in solution by using potentiometry, luminescence spectrometry, and EXAFS. Three series of successive complexes were characterized by at least two of these methods: the immediate [LnHn(dota)](n-1)+** and intermediate [LnHn(dota)](n-1)+* complexes with 0 相似文献   

Utilization of IR spectral detailed analysis for coordination mode determination in novel Zn-cyclen-aminoacid complexes

The infrared spectra, elemental and thermal (TG/DTG and DTA) analyses of novel [Zn(cyclen-κ4N1,4,7,10)(HGly-κ2O,O')](ClO4)2 (1), and [Zn2(cyclen-κ4N1,4,7,10)2(μ-S-Ala-κ2N,O)](ClO4)(3)·2H2O (2) complexes (cyclen - 1,4,7,10-tetraazacyclododecane) were recorded and analyzed in the relation to their structural peculiarities. IR spectral data indicate both mono- or bidentate coordination mode of a carboxylate group in the prepared complexes (at pH≈9). The results indicate unusual bidentate carboxylate coordination mode (in complex (1)) toward to Zn2+-cyclen unit. Therefore the crystal structure determination of the crystalline complex [Zn(cyclen-κ4N1,4,7,10)(NO3-κ2O,O')](NO3) was attached in order to support the coordination mode assignment in complex (1).     

Eu(III) macrocyclic complexes promote cleavage of and bind to models for the 5'-cap of mRNA. Effect of pendent group and a second metal ion

The interaction of three Eu(III) macrocyclic complexes Eu(THED)3+, Eu(ATHC)3+, and Eu(ATHC)3+, and Eu(S-THP)3+ with two 5'-cap model compounds, GpppG and m7GpppG is studied (THED = 1,4,7,10-tetrakis(2-hydroxyethyl)-1,4,7,-10-tetraazacyclododecane, ATHC = 1-(carbamoylmethyl)-4,7,10-tris(2-hydroxyethyl)-1,4,7,10- tetraazacyclododecane, S-THP = 1S,4S,7S,10S-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane). Laser-induced excitation luminescence spectroscopy is used to study the binding of Eu(S-THP)3+ to GpppG (K = 5.9 x 10(4) M-1) and to characterize the Eu(S-THP)-GpppG complex. Both Eu(THED)3+ and Eu(S-THP)3+ bind to m7GpppG as monitored by use of fluorescence spectroscopy with binding constants of 5.9 x 10(3) and 4.4 x 10(4) M-1, respectively. The kinetics of cleavage of GpppG by two macrocyclic complexes is studied. Cleavage of GpppG by Eu(THED)3+ is accelerated by 15-fold in the presence of an equivalent of Zn(NO3)2 at pH 7.3, 37 degrees C, suggesting that two metal ions accelerate the cap cleavage reaction. Eu(ATHC)3+ promotes cleavage of GpppG with a pseudo-first-order rate constant of 2.6 x 10(-5) s-1 at pH 7.3, 37 degrees C, and 0.30 mM complex.     

Dinuclear cyano complexes of cobalt(III) and Iron(III) containing noninnocent 1,2,4,5-tetrakis(2-pyridinecarboxamido)benzene bridging ligands

Two new dinucleating ligands 1,2,4,5-tetrakis(2-pyridinecarboxamido)benzene, H(4)(tpb), and 1,2,4,5-tetrakis(4-tert-butyl-2-pyridinecarboxamido)benzene, H(4)(tbpb), have been synthesized, and the following dinuclear cyano complexes of cobalt(III) and iron(III) have been isolated: Na(2)[Co(III)(2)(tpb)(CN)(4)] (1); [N(n-Bu)(4)](2)[Co(III)(2)(tbpb)(CN)(4)] (2); [Co(III)(2)(tbpb(ox2))(CN)(4)] (3); [N(n-Bu)(4)](2)[Fe(III)(2)(tpb)(N(3))(4)] (4); [N(n-Bu)(4)](2)[Fe(III)(2)(tpb)(CN)(4)] (5); [N(n-Bu)(4)](2)[Fe(III)(2)(tbpb)(CN)(4)] (6). Complexes 2-4 and 6 have been structurally characterized by X-ray crystallography at 100 K. From electrochemical and spectroscopic (UV-vis, IR, EPR, M?ssbauer) and magnetochemical investigations it is established that the coordinated central 1,2,4,5-tetraamidobenzene entity in the cyano complexes can be oxidized in two successive one-electron steps yielding paramagnetic (tbpb(ox1))(3)(-) and diamagnetic (tbpb(ox2))(2)(-) anions. Thus, complex 6 exists in five characterized oxidation levels: [Fe(III)(2)(tbpb(ox2))(CN)(4)](0) (S = 0); [Fe(III)(2)(tbpb(ox1))(CN)(4)](-) (S = (1)/(2)); [Fe(III)(2)(tbpb)(CN)(4)](2)(-) (S = 0); [Fe(III)Fe(II)(tbpb)(CN)(4)](3)(-) (S = (1)/(2)); [Fe(II)(2)(tbpb)(CN)(4)](4)(-) (S = 0). The iron(II) and (III) ions are always low-spin configurated. The electronic structure of the paramagnetic iron(III) ions and the exchange interaction of the three-spin system [Fe(III)(2)(tbpb(ox1))(CN)(4)](-) are characterized in detail. Similarly, for 2 three oxidation levels have been identified and fully characterized: [Co(III)(2)(tbpb)(CN)(4)](2)(-) (S = 0); [Co(III)(2)(tbpb(ox1))(CN)(4)](-) (S = (1)/(2)); [Co(III)(2)(tbpb(ox2))(CN)(4)](0). The crystal structures of 2 and 3 clearly show that the two electron oxidation of 2 yielding 3 affects only the central tetraamidobenzene part of the ligand.     

Discrete Rh(III)/Fe(II) and Rh(III)/Fe(II)/Co(III) cyanide-bridged mixed valence compounds

The heterotrinuclear complexes trans- and cis-[{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) are unprecedented examples of mixed valence complexes based on ferrocyanide bearing three different metal centers. These complexes have been assembled in a stepwise manner from their {trans-III-L(14S)Co(III)}, {cis-VI-L(15)Rh(III)}, and {Fe(II)(CN)(6)} building blocks. The preparative procedure follows that found for other known discrete assemblies of mixed valence dinuclear Cr(III)/Fe(II) and polynuclear Co(III)/Fe(II) complexes of the same family. A simple slow substitution process of [Fe(II)(CN)(6)](4-) on inert cis-VI-[Rh(III)L(15)(OH)](2+) leads to the preparation of the new dinuclear mixed valence complex [{cis-VI-L(15)Rh(III)(μ-NC)}Fe(II)(CN)(5)](-) with a redox reactivity that parallels that found for dinuclear complexes from the same family. The combination of this dinuclear precursor with mononuclear trans-III-[Co(III)L(14S)Cl](2+) enables a redox-assisted substitution on the transient {L(14S)Co(II)} unit to form [{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+). The structure of the final cis-[{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) complex has been established via X-ray diffraction and fully agrees with its solution spectroscopy and electrochemistry data. The new species [{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) and [{cis-VI-L(15)Rh(III)(μ-NC)}Fe(II)(CN)(5)](-) show the expected electronic spectra and electrochemical features typical of Class II mixed valence complexes. Interestingly, in the trinuclear complex, these features appear to be a simple addition of those for the Rh(III)/Fe(II) and Co(III)/Fe(II) moieties, despite the vast differences existent in the electronic spectra and electrochemical properties of the two isolated units.     

Imidazole and imidazolate iron complexes: on the way for tuning 3D-structural characteristics and reactivity. Redox interconversions controlled by protonation state

X-ray structures for six Fe(II) and Fe(III) complexes from two closely heptadentate N-tripodal ligands, L1H(3) = tris[(imidazol-4-yl)-3-aza-3-butenyl]amine and L2H(3) = tris[(imidazol-2-yl)-3-aza-3-butenyl]amine, are described: three complexes in the L1 series (namely, [Fe(II)(L1H(3))](2+) and [Fe(III)(L1H(3))](3+) at low pH and [Fe(III)(L1)](0) at high pH) and three complexes in the L2 series (namely, [Fe(II)(L2H(3))](2+) at low pH and [Fe(II)(L2H)](0) and [Fe(III)(L2)](0) at high pH). Most of these complexes are stable in both Fe(II) and Fe(III) redox states and with the ligand in various protonation states. In the solid state, hydrogen bonds networks were obtained. Structural differences induced by 2- or 4-imidazole substitution are described and discussed. In solution, interconversions between different forms, with regard to oxidation and protonation states, were investigated by UV-visible spectroscopy, cyclic voltammetry, and potentiometry. The deprotonation pattern of these polyimidazole iron(II) and iron(III) complexes is described in detail. pK(a)s of the imidazolate/imidazole moieties in MeOH/H(2)O are reported. Two new species, namely, [Fe(II)(L1)](-) and [Fe(II)(L2)](-), were shown to be obtained in DMSO upon strong base addition and characterized by UV-vis spectroscopy and cyclic voltammetry. Half-wave potentials of Fe(III)/Fe(II) complexes with ligand moieties in several protonation states are reported, both in DMSO and in MeOH/H(2)O. Because of the presence of free imidazole groups coordinated to the iron, the potential of the iron(III)/iron(II) couples can be tuned by pH. A shift of DeltaE = E(deprot) - E(prot) ranging from -270 to -320 mV per exchanged proton in DMSO was measured. This study shows moreover that interconversions (with regard to both redox and protonation states) can be reversed several times. As the complexes have been isolated in order to be tested as superoxide dismutase mimics, preliminary reactions with dioxygen and with superoxide, considered as oxidant and reducer of biological importance, are reported. In these two series, O(2)(-) behaves either as a base or as a reducer and no adducts have been observed.     

Relaxivity and water exchange studies of a cationic macrocyclic gadolinium(III) complex

We conducted relaxometric and water exchange studies of the cationic [Gd((S,S,S,S)-THP)(H2O)]3+ complex (THP 1,4,7,10-tetrakis(2-hydroxy-propyl)-1,4,7,10-tetraazacyclododecane). While the NMRD profiles obtained are typical for DOTA-like complexes (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate), variable-temperature 7O NMR investigations revealed a relatively high water exchange rate (k(298)(ex) = 1.89 x 10(7) s(-1)). These results differ from those reported for other cationic tetraamide macrocyclic Gd(III) complexes, which exhibit characteristically low exchange rates. Since the low exchange rates are attributed partially to the geometry of the M isomer (square antiprismatic) in the tetraamide derivatives, the atypical water exchange rate observed in [Gd((S,S,S,S)-THP-(H2O)]3+ may result from a twisted square antiprismatic structure in this complex and from the relatively high steric strain at the water coordination site as a result of the presence of methyl groups at the alpha-position with respect to the Gd(III)-bound O atoms of THP.     

Metal ion-dependent molecular inclusion chemistry: inclusion of aromatic anions by coordinated 1,4,7,10-tetrakis((S)-2-hydroxy-3-phenoxypropyl)-1,4,7,10-tetraazacyclododecane

The ability of the pendant donor macrocyclic ligand 1,4,7,10-tetrakis((S)-2-hydroxy-3-phenoxypropyl)-1,4,7,10-tetraaza- cyclododecane((S)-thphpc12) (or [Cd((S)-thphpc12)](2+)) to act as a metal ion-dependent receptor for aromatic anions has been investigated in solution and in the solid state. [Cd((S)-thphpc12)](2+) adopts a stable conical conformation with a large hydrophobic cavity, which has been shown to contain, via complementary multiple hydrogen bonding, p-nitrophenolate, aromatic carboxylates, p-toluenesulfonate, certain aromatic amino acid anions, phenoxyacetate, and acetate. In the case of p-nitrophenolate only, one or two anions can be contained within the receptor cavity. The crystal structure of [Cd((S)-thphpc12)(p-nitrophenolate)(2)] shows a coplanar arrangement of the p-nitrophenolates, where each is retained in the cavity by a pair of hydrogen bonds to cis hydroxyl groups. The crystal structure of the p-aminobenzoate inclusion complex indicates retention of the guest via a pair of hydrogen bonds to each oxygen atom of the carboxylate moiety. The crystal structure of the (L)-phenylalaninate inclusion complex indicates that the amino acid is retained by five hydrogen bonds, two involving the nitrogen atom and three to the oxygen atoms of the carboxylate moiety. Binding constants (10(3)-10(5) M(-1)) for the inclusion of some of the aforementioned anions in [Cd((S)-thphpc12)](2+) and related receptors were measured by (1)H NMR titration in DMSO-d(6) at 298 K.     

A new zinc(II) fluorophore 2-(9-anthrylmethylamino)ethyl-appended 1,4,7,10-tetraazacyclododecane

A new 2-(9-anthrylmethylamino)ethyl-appended cyclen, L(3) (1-(2-(9-anthrylmethylamino)ethyl)-1,4,7,10-tetraazacyclododecane) (cyclen = 1,4,7,10-tetraazacyclododecane), was synthesized and characterized for a new Zn(2+) chelation-enhanced fluorophore, in comparison with previously reported 9-anthrylmethylcyclen L(1) (1-(9-anthrylmethyl)-1,4,7,10-tetraazacyclododecane) and dansylamide cyclen L(2). L(3) showed protonation constants log K(a)(i)() of 10.57 +/- 0.02, 9.10 +/- 0.02, 7.15 +/- 0.02, <2, and <2. The log K(a3) value of 7.15 was assigned to the pendant 2-(9-anthrylmethylamino)ethyl on the basis of the pH-dependent (1)H NMR and fluorescence spectroscopic measurements. The potentiometric pH titration study indicated extremely stable 1:1 Zn(2+)-L(3) complexation with a stability constant log K(s)(ZnL(3)) (where K(s)(ZnL(3)) = [ZnL(3)]/[Zn(2+)][L(3)] (M(-)(1))) of 17.6 at 25 degrees C with I = 0.1 (NaNO(3)), which is translated into the much smaller apparent dissociation constant K(d) (=[Zn(2+)](free)[L(3)](free)/[ZnL(3)]) of 2 x 10(-)(11) M with respect to 5 x 10(-)(8) M for L(1) at pH 7.4. The quantum yield (Phi = 0.14) in the fluorescent emission of L(3) increased to Phi = 0.44 upon complexation with zinc(II) ion at pH 7.4 (excitation at 368 nm). The fluorescence of 5 microM L(3) at pH 7.4 linearly increased with a 0.1-5 microM concentration of zinc(II). By comparison, the fluorescent emission of the free ligand L(1) decreased upon binding to Zn(2+) (from Phi = 0.27 to Phi = 0.19) at pH 7.4 (excitation at 368 nm). The Zn(2+) complexation with L(3) occurred more rapidly (the second-order rate constant k(2) is 4.6 x 10(2) M(-)(1) s(-)(1)) at pH 7.4 than that with L(1) (k(2) = 5.6 x 10 M(-)(1) s(-)(1)) and L(2) (k(2) = 1.4 x 10(2) M(-)(1) s(-)(1)). With an additionally inserted ethylamine in the pendant group, the macrocyclic ligand L(3) is a more effective and practical zinc(II) fluorophore than L(1).     

From one-dimensional chain to pentanuclear molecule. Magnetism of cyano-bridged Fe(III)-Ni(II) complexes

Two cyano-bridged Ni(II)-Fe(III) complexes [(H(3)O)[Ni(H(2)L)](2)[Fe(CN)(6)](2).[Fe(CN)(6)].6H(2)O](n) (1) and [K(18-C-6)(H(2)O)(2)][Ni(H(2)L)](2)[Fe(CN)(6)](3).4(18-C-6).20H(2)O (2) (L = 3,10-bis(2-aminoethyl)-1,3,6,8,10,12-hexaazacyclotetradecane, 18-C-6 = 18-crown-6-ether) have been synthesized and characterized structurally and magnetically. Complex 1 has a zigzag one-dimensional structure, in which two trans-CN(-) ligands of each [Fe(CN)(6)](3)(-) link two trans-[Ni(H(2)L)](4+) groups, and in turn, each trans-[Ni(H(2)L)](4+) links two [Fe(CN)(6)](3)(-) in a trans fashion. Complex 2 is composed of cyano-bridged pentanuclear molecules with moieties connected by the trans-CN(-) ligands of [Fe(CN)(6)](3)(-). Magnetic studies show the existence of ferromagnetic Ni(II)-Fe(III) interactions in both complexes. The intermetallic magnetic coupling constant of both complexes was analyzed by using an approximate model on the basis of the structural features.     

Synthesis, structure, and solution properties of [(mim-TASN)FeCl2]+ and its μ-oxo derivative

A series of iron(III) complexes based on the tetradentate ligand 4-((1-methyl-1H-imidazol-2-yl)methyl)-1-thia-4,7-diazacyclononane (L) has been synthesized, and their solution properties investigated. Addition of FeCl(3) to methanol solutions of L yields [LFeCl(2)]FeCl(4) as a dark red solid. X-ray crystallographic analysis reveals a pseudo-octahedral environment around iron(III) with the three nitrogen donors of L coordinated facially. Ion exchange reactions with NaPF(6) in methanol facilitate chloride exchange resulting in a different diastereomer for the [LFeCl(2)](+) cation. X-ray analysis of [LFeCl(2)]PF(6) finds meridional coordination of the three nitrogen donors of L. Electrochemical studies of [LFeCl(2)](+) in acetonitrile display a single Fe(III)/(II) reduction potential at -280 mV versus ferrocenium/ferrocene. In methanol, a broad cathodic wave is observed because of partial exchange of one chloride for methoxide with half-potentials of -170 mV and -440 mV for [LFeCl(2)](+/0) and [LFeCl(OCH(3))](+/0), respectively. The equilibrium constants for chloride exchange are 7 × 10(-4) M(-1) for Fe(III) and 2 × 10(-8) M(-1) for Fe(II). In aqueous solutions chloride exchange yields three accessible complexes as a function of pH. Strongly acidic conditions yield the aqua complex [LFeCl(OH(2))](2+) with a measured pK(a) of 3.8 ± 0.1. Under mildly acidic conditions, the μ-OH complex [(LFeCl)(2)(OH)](3+) with a pK(a) of 6.1 ± 0.3 is obtained. The μ-oxo complex [(LFeCl)(2)(O)](2+) is favored under basic conditions. The diiron Fe(III)/Fe(III) complexes [(LFeCl)(2)(OH)](3+) and [(LFeCl)(2)(O)](2+) can be reduced by one electron to the mixed valence Fe(III)/Fe(II) derivatives at -170 mV and -390 mV, respectively. From pH dependent voltammetric studies, the pK(a) of the mixed valent μ-OH complex [(LFeCl)(2)(OH)](2+) is calculated at 10.3.     

Tethered dinuclear europium(III) macrocyclic catalysts for the cleavage of RNA

Dinuclear europium(III) complexes of the macrocycles 1,3-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-m-xylene (1), 1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene (2), and mononuclear europium(III) complexes of macrocycles 1-methyl-,4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (3), 1-[3'-(N,N-diethylaminomethyl)benzyl]-4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (4), and 1,4,7-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (5) were prepared. Studies using direct excitation ((7)F0 --> (5)D0) europium(III) luminescence spectroscopy show that each Eu(III) center in the mononuclear and dinuclear complexes has two water ligands at pH 7.0, I = 0.10 M (NaNO3) and that there are no water ligand ionizations over the pH range of 7-9. All complexes promote cleavage of the RNA analogue 2-hydroxypropyl-4-nitrophenyl phosphate (HpPNP) at 25 degrees C (I = 0.10 M (NaNO3), 20 mM buffer). Second-order rate constants for the cleavage of HpPNP by the catalysts increase linearly with pH in the pH range of 7-9. The second-order rate constant for HpPNP cleavage by the dinuclear Eu(III) complex (Eu2(1)) at pH 7 is 200 and 23-fold higher than that of Eu(5) and Eu(3), respectively, but only 7-fold higher than the mononuclear complex with an aryl pendent group, Eu(4). This shows that the macrocycle substituent modulates the efficiency of the Eu(III) catalysts. Eu2(1) promotes cleavage of a dinucleoside, uridylyl-3',5'-uridine (UpU) with a second-order rate constant at pH 7.6 (0.021 M(-1) s(-1)) that is 46-fold higher than that of the mononuclear Eu(5) complex. Methyl phosphate binding to the Eu(III) complexes is energetically most favorable for the best catalysts, and this supports an important role for the catalyst in stabilization of the developing negative charge on the phosphorane transition state. Despite the formation of a bridging phosphate ester between the two Eu(III) centers in Eu2(1) as shown by luminescence spectroscopy, the two metal ion centers are only weakly cooperative in cleavage of RNA and RNA analogues.     

Hydrogen-bonding cavities about metal ions: synthesis, structure, and physical properties for a series of monomeric M-OH complexes derived from water

The tripodal ligand N[CH2CH2NHC(O)NHC(CH3)3]3 ([H61]) was used to synthesize a series of monomeric complexes with terminal hydroxo ligands. The complexes [Co(II/III)H31(OH)](2-/1-), [Fe(II/III)H31(OH)](2-/1-), and [Zn(II)H31(OH)](2-) have been isolated and characterized. The source of the hydroxo ligand in these complexes is water, which was confirmed with an isotopic labeling study for [Co(III)H31(OH)](1-). The synthesis of [M(II)H31(OH)](2-) complexes was accomplished by two routes. Method A used 3 equiv of base prior to metalation and water binding, affording yields of < or = 40% for [Co(II)H31(OH)](2-). When 4 equiv of base was used (method B), yields ranged from 50% to 70% for all of the M(II)H31(OH)](2-) complexes. This improvement is attributed to the presence of an intramolecular basic site within the cavity, which scavenges protons produced during formation of the M(II)-OH complexes. The molecular structures of [Zn(II)H31(OH)](2-), [Fe(II)H31(OH)](2-), [Co(II)H31(OH)](2-), and [Co(III)H31(OH)](1-) were examined by X-ray diffraction methods. The complexes have trigonal bipyramidal coordination geometry with the hydroxo oxygen trans to the apical nitrogen. The three M(II)-OH complexes crystallized with nearly identical lattice parameters, and each contains two independent anions in the asymmetric unit. The complexes have intramolecular H-bonds from the urea cavity of [H31](3-) to the coordinated hydroxo oxygen. All the complexes have long M-O(H) bond lengths (>2.00 A) compared to those of the few previously characterized synthetic examples. The longer bond distances in [M(II)H31(OH)](2-) reflect the intramolecular H-bonds in the complexes. The five-coordinate [Zn(II)H31(OH)](2-) has an average Zn-O(H) distance of 2.024(2) A, which is similar to that found for the zinc site in carbonic anhydrase II (2.05(2) A). The enzyme active site also has an extensive network of intramolecular H-bonds to the hydroxo oxygen. [Co(II)H31(OH)](2-) and [Fe(II)H31(OH)](2-) have one-electron redox processes at -0.74 and -1.40 V vs SCE. Both complexes can be chemically oxidized to yield their corresponding M(III)-OH complexes. [Co(III)H31(OH)](1-), with an S = 1 ground state, is a rare example of a paramagnetic Co(III) complex.