Demetallation of a Ni(II) tetraazamacrocyclic complex by cyanoxime resulting in the formation of a stereospecific trinuclear compound [Na(H2O)6]+[NaNi2L6]− (L = NC-C(NO)-C(O)NH )

Gerasimchuk, Nikolay; Dalley, N. Kent

doi:10.1080/00958970412331312652

Cited by 29 publications

(11 citation statements)

References 39 publications

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“…The results of the EXAFS studies are shown in ESI 38,39 and demonstrate a very good fit (within 1 – 7 % values) between calculated and experimentally determined parameters of bond length and intera-tomic distances. The model used for the fit had a bidentate cyanoxime anion binding Pt, with the formation of a five-membered chelate ring in a fashion similar to that found in Pd(II) 36 and Ni(II) 65 cyanoximates. Determined by the EXAFS method and data fitting Pt-N and Pt-O bonds are slightly shorter than those experimentally observed in yellow monomeric Pt(PiPCO) 2 and Pt(MCO) 2 (Table 2), which may suggest a rather tighter binding of the equatorial cyanoxime anion to the metal center in the dark-green 1D polymer.…”

Section: Resultsmentioning

confidence: 99%

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

et al. 2017

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Several complexes of “PtL2” composition containing two cyanoxime anions – 2-oximino-2-cyano-N-piperidineacetamide (PiPCO−) and 2-oximino-2-cyano-N-morpholylacetamide (MCO−) have been obtained and characterized both in solutions and in solid state. Complexes exist as two distinct polymorphs: monomeric yellow complexes, and dark-green [PtL2]n 1D polymers, while for the MCO− anion a red, solvent containing dimeric [Pt(MCO)2xDMSO]2 complex also has been isolated. The interconversion of polymorphs was investigated. The monomeric PtL2 units are arranged into the anisotropic extended solid [PtL2]n polymers with the help of Pt—Pt metallophilic interactions. Crystal structures of monomeric PtL2 (L= PiPCO−, MCO−) and red dimeric [Pt(MCO)2xDMSO]2 complexes were determined and revealed the cis-arrangement of cyanoxime anions. The Pt-Pt distance in the “head-to-tail” red dimer was found to be 3.133 Å. The structure of polymeric [Pt(PiPCO)2]n compound was elucidated using the EXAFS method and evidenced the formation of the Pt-wire with ~3.15 Å intermetallic separations. The EPR spectra of both 1D polymers at variable temperatures indicate the absence of Pt(III) species. Both pure dark-green [PtL2]n polymers showed considerable room temperature electrical conductivity of 20–30 S/cm, which evidences the formation of mixed valence Pt(II)/Pt(IV) system. We discovered that these 1D polymeric [PtL2]n complexes show an intense NIR fluorescence beyond 1000 nm, while yellow monomeric PtL2 complexes are not emissive at all. The room temperature excitation spectra of 1D polymeric [PtL2]n complexes demonstrated their strong emission beyond 1000 nm regardless of the used excitation wavelength between 350 and 800 nm, which is typical of systems with delocalized charge carriers. For the first time the formation of mixed valence “metal wire” assembled by metallophilic interactions is directly linked both with an intense fluorescence in the NIR region of spectrum and the electrical conductivity. The effect of concentration of [PtL2]n complexes dispersed in the dielectric salt matrix on the photoluminescence wavelength and intensity was investigated. Both polymers show a remarkably high for this region of spectrum quantum yield reaching ~2%. Variable temperature emission of polymeric [PtL2]n in the −190 - +60°C range was studied as well.

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Section: Resultsmentioning

confidence: 99%

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

et al. 2017

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“…The water exclusion zones and the second coordination shells are marked by gray and blue rectangles, respectively. (B) Ultra-high-accuracy X-ray structures of Mg(H 2 O) 6 2+ (top) and Na(H 2 O) 6 + (bottom) illustrating similarities between Mg 2+ and Na + octahedral first hydration shells (Gerasimchuk and Dalley 2004;Hennings et al 2013). (C ) In scale schematic representation of the radius of the Mg(H 2 O) 6 2+ (green) and Na(H 2 O) 6 + (magenta) first cordination shells.…”

Section: Pdb Overview Of Direct Mg 2+ To Carbonyl Oxygen Atom (O B ) mentioning

confidence: 99%

Nucleobase carbonyl groups are poor Mg²⁺inner-sphere binders but excellent monovalent ion binders—a critical PDB survey

Leonarski

D’Ascenzo

Auffinger

2018

RNA

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Precise knowledge of Mg 2+ inner-sphere binding site properties is vital for understanding the structure and function of nucleic acid systems. Unfortunately, the PDB, which represents the main source of Mg 2+ binding sites, contains a substantial number of assignment issues that blur our understanding of the functions of these ions. Here, following a previous study devoted to Mg 2+ binding to nucleobase nitrogens, we surveyed nucleic acid X-ray structures from the PDB with resolutions ≤2.9 Å to classify the Mg 2+ inner-sphere binding patterns to nucleotide carbonyl, ribose hydroxyl, cyclic ether, and phosphodiester oxygen atoms. From this classification, we derived a set of "prior-knowledge" nucleobase Mg 2+ binding sites. We report that crystallographic examples of trustworthy nucleobase Mg 2+ binding sites are fewer than expected since many of those are associated with misidentified Na + or K +. We also emphasize that binding of Na + and K + to nucleic acids is much more frequent than anticipated. Overall, we provide evidence derived from X-ray structures that nucleobases are poor inner-sphere binders for Mg 2+ but good binders for monovalent ions. Based on strict stereochemical criteria, we propose an extended set of guidelines designed to help in the assignment and validation of ions directly contacting nucleobase and ribose atoms. These guidelines should help in the interpretation of X-ray and cryo-EM solvent density maps. When borderline Mg 2+ stereochemistry is observed, alternative placement of Na + , K + , or Ca 2+ must be considered. We also critically examine the use of lanthanides (Yb 3+ , Tb 3+) as Mg 2+ substitutes in crystallography experiments.

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“…36−38 There were only a few reported complexes of Cu and Ni with cyanoximes in general, with most of them being mononuclear compounds. 39−43 With the exception of one dicopper, 41 one stereospecific dinickel, 44 and one octa-iron 45 complex, no other homometallic or heterometallic complexes containing cyanoximes are reported. The 2-cyano-2-hydroxyimino-ethyl acetate, which is commercially known as "Oxyma" (HECO), and its analogous compound 2-cyano-2-hydroxyimino-methyl acetate (HMeCO) represent inexpensive and easily accessible compounds.…”

Section: ■ Introductionmentioning

confidence: 99%

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

Opalade

Gómez‐García

Gerasimchuk

2019

Crystal Growth & Design

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A series of new polynuclear complexes of divalent Ni and Cu with 2-cyano-2-oximino-acetic acid (later AACO2-) were obtained as the result of the ligand modification reaction in the process of complexation, using 2-cyano-2-oximino-acetates such as methyl- (later as MeCO), and ethyl- (as ECO later on). Synthesized compounds were characterized by spectroscopic methods, thermal analysis, magnetochemistry, and X-ray crystallography. Crystal data revealed the formation of the dimeric [Ni(AACO)(H2O)3]2·H2O (1), trimeric K2[Ni3(AACO)4(H2O)4]·4H2O (2), and K2[Cu3(AACO)4(H2O)4]·4H2O (3) complexes, with bridging NO-groups cyanoxime dianions. In the latter two compounds, the AACO2– anions adopt cis-arrangements around metal centers. One mononuclear complex of K2[Cu(AACO)2(H2O)]·2H2O (4) composition was isolated and characterized as well, where the cyanoxime forms the trans-complex 4. There is moderate-to-strong antiferromagnetic coupling between metal centers in polynuclear complexes. Data of thermal analysis studies revealed high-energy properties for dehydrated complexes 3 and 4, which violently decompose at ∼200 °C. These compounds may be viewed as room temperature completely safe, but heat-triggered actuators, because of their pronounced mechanical action upon leaving the system (crucible). Final products of thermal decomposition are Ni and NiO for 1, and the mixture of NiO and K2O for 2, with metallic copper for 3 and 4.

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Demetallation of a Ni(II) tetraazamacrocyclic complex by cyanoxime resulting in the formation of a stereospecific trinuclear compound [Na(H₂O)₆]⁺[NaNi₂L₆]⁻ (L = NC-C(NO)-C(O)NH )

Cited by 29 publications

References 39 publications

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

Nucleobase carbonyl groups are poor Mg²⁺inner-sphere binders but excellent monovalent ion binders—a critical PDB survey

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

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Demetallation of a Ni(II) tetraazamacrocyclic complex by cyanoxime resulting in the formation of a stereospecific trinuclear compound [Na(H2O)6]+[NaNi2L6]− (L = NC-C(NO)-C(O)NH )

Cited by 29 publications

References 39 publications

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

Nucleobase carbonyl groups are poor Mg2+inner-sphere binders but excellent monovalent ion binders—a critical PDB survey

New Route to Polynuclear Ni(II) and Cu(II) Complexes with Bridging Oxime Groups That Are Inaccessible by Conventional Preparations

Contact Info

Product

Resources

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Demetallation of a Ni(II) tetraazamacrocyclic complex by cyanoxime resulting in the formation of a stereospecific trinuclear compound [Na(H₂O)₆]⁺[NaNi₂L₆]⁻ (L = NC-C(NO)-C(O)NH )

Nucleobase carbonyl groups are poor Mg²⁺inner-sphere binders but excellent monovalent ion binders—a critical PDB survey