Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.

A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins.     

Towards the rational design of MRI contrast agents: electron spin relaxation is largely unaffected by the coordination geometry of gadolinium(III)-DOTA-type complexes

Electron-spin relaxation is one of the determining factors in the efficacy of MRI contrast agents. Of all the parameters involved in determining relaxivity it remains the least well understood, particularly as it relates to the structure of the complex. One of the reasons for the poor understanding of electron-spin relaxation is that it is closely related to the ligand-field parameters of the Gd(3+) ion that forms the basis of MRI contrast agents and these complexes generally exhibit a structural isomerism that inherently complicates the study of electron spin relaxation. We have recently shown that two DOTA-type ligands could be synthesised that, when coordinated to Gd(3+), would adopt well defined coordination geometries and are not subject to the problems of intramolecular motion of other complexes. The EPR properties of these two chelates were studied and the results examined with theory to probe their electron-spin relaxation properties.     

Probing the N(5)-H bond of the isoalloxazine moiety of flavin radicals by X- and W-band pulsed electron-nuclear double resonance.

An X- (9.7 GHz and W-band (94 GHz) pulsed electron-nuclear double resonance (ENDOR) study of the flavin cofactor of Escherichia coli DNA photolyase in its neutral radical form is presented. Through proton and deuteron ENDOR measurements at T = 80 K, we detect and characterize the full anisotropy of the hyperfine coupling (hfc) tensor of the proton or deuteron bound to N(5) of the isoalloxazine ring. Scaling of the anisotropic proton hfc components by multiplication with the quotient of the magnetogyric ratio of a deuteron and a proton, chiD/chiH, reveals subtle differences compared to the respective deuteron couplings obtained by 95-GHz deuterium ENDOR spectroscopy on an H-->D buffer-exchanged sample. These differences can be attributed to the different lengths of N(5)-H and N(5)-D bonds arising from the different masses of protons and deuterons. From the R(-3) dependence of the dipolar hyperfine splitting, we estimated that the N(5)-D bond is about 2.5% shorter than the respective N(5)-H bond. That such subtle bond-length differences can be resolved by pulsed ENDOR spectroscopy suggests that this method may be favorably used to probe the geometry of hydrogen bonds between the H(5) of the paramagnetic flavin and the protein backbone. Such information is only obtained with difficulty by other types of spectroscopy.     

A family of four-coordinate iron(II) complexes bearing the sterically hindered tris(pyrazolyl)borato ligand Tp(tBu,Me)

A new family of 14‐electron, four‐coordinate iron(II) complexes of the general formula [Tp^tBu,MeFeX] (Tp^tBu,Me is the sterically hindered hydrotris(3‐tert‐butyl‐5‐methyl‐pyrazolyl) borate ligand and X=Cl ( 1 ), Br, I) were synthesized by salt metathesis of FeX₂ with Tp^tBu,MeK. The related fluoride complex was prepared by reaction of 1 with AgBF₄. Chloride 1 proved to be a good precursor for ligand substitution reactions, generating a series of four‐coordinate iron(II) complexes with carbon, oxygen, and sulphur ligands. All of these complexes were fully characterized by conventional spectroscopic methods and most were characterized by single‐crystal X‐ray crystallographic analysis. Magnetic measurements for all complexes agreed with a high‐spin (d⁶, S=2) electronic configuration. The halide series enabled the estimation of the covalent radius of iron in these complexes as 1.24 Å.     

Lanthanide(III) complexes of a mono(methylphosphonate) analogue of H4dota: the influence of protonation of the phosphonate moiety on the TSAP/SAP isomer ratio and the water exchange rate

A monophosphonate analogue of H4dota, 1,4,7,10-tetraazacyclododecane-4,7,10-tris(carboxymethyl)-1-methylphosphonic acid (H5do3aP), and its complexes with lanthanides were synthesized. Multinuclear NMR studies reveal that, in aqueous solution, lanthanide(III) complexes of the ligand exhibit structures analogous to those of H4dota complexes. Thus, the central ion is nine-coordinate, surrounded by four nitrogen atoms, three acetate and one phosphonate oxygen atoms, and one water molecule in an apical position. For complexes of H5do3aP with Ln(III) ions in the middle of the series, the abundance of the desired twisted square-antiprismatic (TSAP) isomer is higher than for the corresponding H4dota complexes. The TSAP/square-antiprismatic (SAP) isomer ratio is highly sensitive to protonation of the phosphonate group: a higher abundance of the TSAP isomer was found in acidic solutions. The microscopic protonation constants of the TSAP isomers are higher than those of the SAP isomers. The presence of one water molecule in the first coordination sphere of the complexes in the pH region studied (pH 2.5-7.0) is confirmed by 17O NMR spectroscopy. The results of a simultaneous fit of variable-temperature 17O NMR relaxation data and 1H NMRD profiles show that the residence time of water (tauM) in the Gd(III) complex is much smaller than for [Gd(dota)(H2O)]-. The exchange rate appears to be dependent on the pH of the solution. The values of tauM are 37, 40, and 14 ns at pH 2.5, 4.7, and 7.0, respectively. These observations can be explained by an extensive second-sphere hydrogen-bonding network that varies with the state of protonation of the phosphonate moiety. Upon protonation of the complex, the second-sphere hydration probably becomes more ordered, which may result in a decrease in penetrability and an increase in tauM. The relaxivity of the Gd(III) complex is almost independent of the pH and is equal to 4.7 s(-1) mM(-1) (20 MHz, pH 7 and 37 degrees C). The solid-state structure was determined for the Nd(III) complex. It crystallizes as the TSAP isomer and the unit cell contains two independent molecules of the complex with different Nd-O(water) bond lengths of 2.499 and 2.591 A.     

Multi‐frequency (S,X, Q and W‐band) EPR and ENDOR Study of Vanadium(IV) Incorporation in the Aluminium Metal–Organic Framework MIL‐53

Doping the well‐known metal–organic framework MIL‐53(Al) with vanadium(IV) ions leads to significant changes in the breathing behaviour and might have repercussions on the catalytic behaviour as well. To understand the properties of such a doped framework, it is necessary to determine where dopant ions are actually incorporated. Electron paramagnetic resonance (EPR) and electron–nuclear double resonance (ENDOR) are applied to reveal the nearest environment of the paramagnetic vanadium(IV) dopant ions. EPR spectra of as‐synthesised vanadium‐doped MIL‐53 are recorded at S‐, X‐, Q‐ and W‐band microwave frequencies. The EPR spectra suggest that at low dopant concentrations (1.0–2.6 mol %) the vanadium(IV) ions are well dispersed in the matrix. Varying the vanadium dopant concentration within this range or the dopant salt leads to the same dominant EPR component. In the ENDOR spectra, hyperfine (HF) interactions with ¹H, ²⁷Al and ⁵¹V nuclei are observed. The HF parameters extracted from simulations strongly suggest that the vanadium(IV) ions substitute Al in the framework.     

Solvatochromism of thiocyanato-tetraazamacrocycle-manganese(III) complexes

Summary Solvent effects on thecharge-transfer bands of a series of thiocyanato-tetraazamacrocycle-manganese(III) complexes are reported, and discussed in terms of the donor and acceptor (hydrogen-bonding) properties of the respective solvents. The piezochromic behaviour of one of these complexes is also described.

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Solvatochromie von Thiocyanato-Tetraazamakrocyclo-Mangan(III) — Komplexen

Zusammenfassung Die Auswirkung von Lösungsmitteleffekten auf diecharge-transfer — Banden einer Reihe von Thiocyanato-Tetraazamakrocyclo-Mangan(III) — Komplexen wird im Zusammenhang mit den Donor- und Akzeptoreigenschaften des Lösungsmittels diskutiert. Das piezochrome Verhalten eines der Komplexe wird beschrieben.

     

A neutron inelastic scattering investigation of the diffusion kinetics of H2O molecules and hydration complexes in concentrated ionic solutions

Intermolecular frequencies of H₂O's and the diffusion kinetics have been investigated by neutron inelastic scattering for concentrated ionic solutions containing small and/or multiply charged cations (e.g., Cr⁺³, Mg⁺², Ca⁺², and Li⁺¹). As higher concentrations are approached such that the majority of H₂O's are in hydration layers, their exchange time can exceed the neutron interaction time. Then the diffusion kinetics depart functionally from activated reorientations of individual H₂O's characteristic of lower concentrations and evolve to continuous diffusion processes of hydration complexes characterized by small self-diffusion coefficients. The general features of the observed evolution in the functionality of the diffusion kinetics are found to be functionally consistent with an approximate model which includes contributions from the delayed diffusional exchange of individual H₂O's as well as the continuous diffusion of hydrated ions. At a given concentration, the temperature interval over which this evolution in functionality occurs increases both with increasing strength of the primary cation-H₂O coordination and with anion basicity. Further, as the temperature decreases, frequencies of defined cation-water hydration complexes gradually sharpen in a continuous manner, showing no abrupt variations at glass transitions. Anions of increasing basicity decrease the self-diffusion coefficients of the ion-water complexes and perturbed frequencies characteristic of cation-water hydration complexes. Such anion effects, at high concentrations, correspond to an increasing degree of time-average indirect or direct ion pairing with increasing anion basicity. This results, in turn, both in a distortion or partial disruption of the cation hydration sheaths and in a degree of coupling and/or bridging between anions and hydrated cations so as to increase the effective masses and friction coefficients associated with their diffusional motions.     

All-cis-1,2,3,4,5,6-cyclohexanehexacarboxylate two-dimensional gadolinium(III) complexes: Synthesis,X-ray crystal structure and magnetic properties

The first gadolinium(III) complexes with the trideprotonated form of the 1,2,3,4,5,6-cyclohexanehexacarboxylic acid (H₃clhex³⁻) of formulae [Gd(H₃clhex)(H₂O)₄]_n·3nH₂O (1) and [Gd(H₃clhex)(H₂O)₄]_n·6nH₂O (2) have been prepared through the gel technique and their structures determined by single crystal X-ray diffraction. The structure of 1 is made up of 6³ honey-comb layers which are generated by [Gd(H₂O)₄]³⁺ cations and H₃clhex³⁻ anions acting as three-fold nodes and three-fold connectors, respectively. The structure of 2 consists of a [4⁴,6²] two-dimensional network extended in the ac plane where the H₃clhex⁻³ groups act as four-fold connectors and the [Gd(H₂O)₄]³⁺ units as four-fold nodes. Compound 1 crystallises in a non-centrosymmetric space group P2₁. Its absolute structure could be determined reliably, indicating the spontaneous resolution of a homochiral crystal and the freezing of one of the conformations of the all-cis H₃clhex⁻³ ligand. Compound 2 crystallises in the P2₁/n space group, the presence of an inversion centre making both conformations to occur. 1 and 2 are different solvates of the same system, the latter one synthesised under a higher pH value of the gel than the former. The investigation of the magnetic properties of 1 and 2 in the temperature range 1.9–300 K reveals a Curie law behaviour for the two compounds.     

Unusual iron(III) ate complexes stabilized by Li-pi interactions

Several iron(III) complexes incorporating diamidoether ligands are described. The reaction between [Li(2)[RN(SiMe(2))](2)O] and FeX(3) (X=Cl or Br; R=2,4,6-Me(3)Ph or 2,6-iPr(2)Ph) form unusual ate complexes, [FeX(2)Li[RN(SiMe(2))](2)O](2) (2, X=Cl, R=2,4,6-Me(3)Ph; 3, X=Br, R=2,4,6-Me(3)Ph; 4, X=Cl, R=2,6-iPr(2)Ph) which are stabilized by Li-pi interactions. These dimeric iron(III)-diamido complexes exhibit magnetic behaviour characteristic of uncoupled high spin (S= 5/2 ) iron(III) centres. They also undergo halide metathesis resulting in reduced iron(II) species. Thus, reaction of 2 with alkyllithium reagents leads to the formation of iron(II) dimer [Fe[Me(3)PhN(SiMe(2))](2)O](2) (6). Similarly, the previously reported iron(III)-diamido complex [FeCl[tBuN(SiMe(2))](2)O](2) (1) reacts with LiPPh(2) to yield the iron(II) dimer [Fe[tBuN(SiMe(2))](2)O](2) but reaction with LiNPh(2) gives the iron(II) product [Fe(2)(NPh(2))(2)[tBuN(SiMe(2))](2)O] (5). Some redox chemistry is also observed as side reactions in the syntheses of 2-4, yielding THF adducts of FeX(2): the one-dimensional chain [FeBr(2)(THF)(2)](n) (7) and the cluster [Fe(4)Cl(8)(THF)(6)]. The X-ray crystal structures of 3, 5 and 7 are described.     

A series of new pyridine carboxamide complexes and self-assemblies with Tb(III), Eu(III), Zn(II), Cu(II) ions and their luminescent and magnetic properties

In this study, we present eight new complexes and self-assemblies of Tb(III), Eu(III), Zn(II) and Cu(II) ions with novel pyridine carboxamides, L1 [methyl 4-methyl-3-(pyridine-4-carbonylamino)benzoate] and L2 [methyl 2-methyl-3-(pyridine-4-carbonylamino)benzoate], as heterocyclic ligands. Two luminescent and spatially organized coordination compounds were obtained with the use of the solvothermal synthesis method, (1) [Tb₃(L1)₄(BTC)₃(H₂O)₃] (where BTC is benzene-1,3,5-tricarboxylic acid) and (5) [Eu(L2a)₃(H₂O)₃](H₂O)₄. As a result of one pot reaction synthesis under reflux the d-electron metal ions and self-organization of ligands gave complexes (2) [Zn(L1)₂Cl₂], (3) [Cu(L1)₂(SCN)₂(H₂O)], (4) [Cu(L1)₂Cl₂], hybrid salt (6) [(CuCl₄)^2-(L2b)₂²⁺](H₂O), (7) [Cu(L2)₂Cl₂] and 1D-chain coordination polymer (8) [Cu(L2)₂(SCN)₂]. Identification of the obtained compounds was performed on the basis of the excitation, emission, ¹H NMR, FT-IR spectra, luminescence lifetimes, SEM images, PXRD, single-crystal X-ray diffraction, MS, TGA and elemental analysis. Selected compounds were also analyzed in terms of their potential magnetic properties.     

Binding modes in metal ion complexes of quinones and semiquinone radical anions: electron-transfer reactivity.

9,10-Phenanthrenequinone (PQ) and 1,10-phenanthroline-5,6-dione (PTQ) form 1:1 and 2:1 complexes with metal ions (M (n+)=Sc (3+), Y (3+), Mg (2+), and Ca (2+)) in acetonitrile (MeCN), respectively. The binding constants of PQ--M (n+) complexes vary depending on either the Lewis acidity or ion radius of metal ions. The one-electron reduced species (PTQ(-)) forms 1:1 complexes with M (n+), and PQ(-) also forms 1:1 complexes with Sc(3+), Mg(2+), and Ca(2+), whereas PQ(-) forms 1:2 complexes with Y(3+) and La(3+), as indicated by electron spin resonance (ESR) measurements. On the other hand, semiquinone radical anions (Q(-) and NQ(-)) derived from p-benzoquinone (Q) and 1,4-naphthoquinone (NQ) form Sc(3+)-bridged pi-dimer radical anion complexes, Q(-)--(Sc(3+))(n)--Q and NQ(-)--(Sc(3+))(n)-NQ (n=2 and 3), respectively. The one-electron reduction potentials of quinones (PQ, PTQ, and Q) are largely positively shifted in the presence of M (n+). The rate constant of electron transfer from CoTPP (TPP(2-)=dianion of tetraphenylporphyrin) to PQ increases with increasing the concentration of Sc(3+) to reach a constant value, when all PQ molecules form the 1:1 complex with Sc(3+). Rates of electron transfer from 10,10'-dimethyl-9,9'-biacridine [(AcrH)(2)] to PTQ are also accelerated significantly by the presence of Sc(3+), Y(3+), and Mg(2+), exhibiting a first-order dependence with respect to concentrations of metal ions. In contrast to the case of o-quinones, unusually high kinetic orders are observed for rates of Sc(3+)-promoted electron transfer from tris(2-phenylpyridine)iridium(III) [Ir(ppy)(3)] to p-quinones (Q): second-order dependence on concentration of Q, and second- and third-order dependence on concentration of Sc(3+) due to formation of highly ordered radical anion complexes, Q()--(Sc(3+))(n)--Q (n=2 and 3).     

Can DFT methods correctly and efficiently predict the coordination number of copper(I) complexes? A case study

The coordination number of various experimentally known Cu(I) compounds is studied using density functional theory. Various basis sets are tested, aiming to establish a reliable level for prediction of the coordination number of these and other Cu(I) complexes. It is found that most levels exhibit correct trends, namely, the bulkier ligands demonstrate larger preference for coordination of two ligands. Proper absolute values are obtained when dispersion corrections are also included in the calculations. It is concluded that the fairly small modified 6‐31+G* basis set due to Pulay represents a good compromise between accuracy and efficiency, followed by Balabanov and Peterson's all‐electron aug‐cc‐pVDZ basis set. The overall energy is decomposed into various components whose relative contribution to the overall tendency of forming a complex with a particular coordination is examined. It is shown that two opposing contributions play a major role: the interaction energy of the ligand being added and the deformation energy of the copper's coordination sphere prior to the ligand addition. The former being a stabilizing contribution, leads to higher coordination numbers while the later, a destabilizing contribution, is shown to favor lower coordination numbers. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010     

"Naked-eye" detection of histidine by regulation of Cu(II) coordination modes

The association of various alpha-amino acids with four new, coordinatively unsaturated metal complexes ([Cu(5)]2+, [Cu(6)]2+, [Cu(7)]2+, and [Zn(8)]2+) was examined. The receptors [Cu(5)]2+ and [Cu(7)]2+ were found to discriminate histidine (His) from other zwitterionic alpha-amino acids by means of indicator-displacement assays (IDAs) using 5(6)-carboxyfluorescein as an indicator in buffered methanol/water (3:1) solvent. The colorimetric detection of His was achieved by using this IDA method, which appears to owe its selectivity to a unique process involving disruption of the host complex to form a 2:1 His/Cu(II) complex rather than simple indicator displacement. The occurrence of distinct intermolecular coordination processes in response to the introduction of a different amino acid is observed. X-ray crystal structures of the host metal complexes were obtained and exhibit the adoption of a variety of coordination geometries about the metal center.     

H- and C-NMR as tools to study aluminium coordination chemistry—aqueous Al(III)-citrate complexes

Based on the use thermodynamic and solid state structure data, ¹H- and ¹³C-NMR is a very useful tool to understand the conformational and dynamic behavior of complexes containing organic ligands in solution. In this paper we describe shortly the possibilities of the assignation of the spectra by means of modern NMR techniques. From the assigned spectra the scalar and dipolar couplings make it possible to determine the orientation of the ligand around the metal ion and the distances between hydrogen atoms in space. Aluminium-citrate complexes are reviewed as examples. It is shown that with the armory of correlation NMR spectroscopy unique insight can be obtained in the behavior of Al-citrate species even if oligomers are present in the solution.