New non-aggregating bivalent cis-ML2 (M = Pd, Pt; L = pivaloylcyanoxime)

Mann, Alexandra; Gerasimchuk, Nikolay; Silchenko, Svitlana

doi:10.1016/j.ica.2015.10.040

Cited by 12 publications

(15 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…All the crystals were placed on plastic MiTeGen holders attached to the copper-pin positioned on the goniometer head of the Bruker APEX-2 diffractometer, equipped with a SMART CCD area detector. The intensity data were collected at room and low temperatures in order to examine the possibility for temperature-dependent polymorphism that has been recently observed in other Pt-cyanoximates, 50 but was not observed in presented in this work complexes. Only low temperature data is presented in this work.…”

Section: Methodsmentioning

confidence: 89%

See 1 more Smart Citation

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

et al. 2017

View full text Add to dashboard Cite

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.

show abstract

Section: Methodsmentioning

confidence: 89%

“…It should be mentioned that the structure of Pt(PiPCO) 2 was determined earlier at 293 K, but we re-grew suitable single crystals and re-determined the structure more accurately at low temperature (100 K) because of the recently observed polymorphism in other Pt-cyanoximates. 50 …”

Section: Resultsmentioning

confidence: 99%

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

et al. 2017

View full text Add to dashboard Cite

show abstract

“…The preparation of the HPiCO was carried out according to previously published procedure, , while the reactions in the cyanoxime–Zn system are presented in Scheme and in a set of equations below. For the preparation of Zn(II) complex, 0.300 g (1.95 mM) of white powdery HPiCO was placed in a beaker containing 5 mL of deionized water, to which 1.95 mL of 1 M KOH solution was added at once.…”

Section: Experimental Partmentioning

confidence: 99%

Zinc Complexes with Cyanoxime: Structural, Spectroscopic, and Catalysis Studies in the Pivaloylcyanoxime–Zn System

et al. 2017

Self Cite

View full text Add to dashboard Cite

Reaction of 2-hydroxyimino-4,4-dimethyl-3-oxo-pentanenitrile (common abbreviation HPiCO, pivaloyl-cyanoxime) with zinc sulfate in an aqueous solution results in the formation of the two new complexes: [Zn(PiCO){H(PiCO)}(HO)] (I) and tetranuclear Zn complex [Zn(μ-OH)(PiCO) (HO)] (II). Both complexes were characterized by elemental analysis, IR- and UV-visible spectra, DSC/TGA studies, and X-ray analysis. In complex II, the PiCO cyanoxime anion adopts three bidentate binding modes: O-monodentate, chelating (κ), and bridging (η) coordinations. Also, the ligand represents the mixture of two diasteromers (cis-anti and cis-syn) that form five- and six-membered chelate rings with Zn atoms and cocrystallize in one unit cell at population of 0.57-0.43. There are two crystallographically different Zn-centers in the ASU, and two μ-bridging hydroxo-groups arrange via inversion center the formation of an elegant tetranuclear complex. Each Zn atom has a molecule of coordinated water and is in the distorted octahedral environment. Because of the structural flexibility and multidentate propensity of the pivaloyl-cyanoxime, complex II may act as a structural model of naturally occurring Zn-containing enzymes. Indeed, compound I exhibits an efficient catalytic performance for transesterification reaction of various esters in ethanol under mild reaction conditions. Therefore, obtained results allow assignment of observed activity as green catalysis.

show abstract

“…In addition, the use of nanotechnology-based drug delivery system is an emerging area of interest for increased payloads, biocompatibility, and targeted delivery of chemotherapeutic drugs, resulting in minimal side effects. Recent studies indicate the huge potential of various nanoparticles as drug carriers in cancer therapy, including targeted drug delivery, diagnosis, imaging, and treatment [38][39][40][41][42][43]. Among others, cerium oxide nanoparticles (NC) has received considerable attention due to its excellent catalytic and antioxidant properties with different cell systems.…”

Section: Introductionmentioning

confidence: 99%

Therapeutic Efficacy of Lactonic Sophorolipids: Nanoceria-Assisted Combination Therapy of NSCLC using HDAC and Hsp90 Inhibitors

et al. 2021

View full text Add to dashboard Cite

New non-aggregating bivalent cis-ML2 (M = Pd, Pt; L = pivaloylcyanoxime)

Cited by 12 publications

References 41 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

Zinc Complexes with Cyanoxime: Structural, Spectroscopic, and Catalysis Studies in the Pivaloylcyanoxime–Zn System

Therapeutic Efficacy of Lactonic Sophorolipids: Nanoceria-Assisted Combination Therapy of NSCLC using HDAC and Hsp90 Inhibitors

Contact Info

Product

Resources

About