The synthesis, thermal and photophysical properties of phenoxycyclotriphosphazenyl-substituted cyclic and polymeric phosphazenes

Çoşut, Bünyemin; Hacıvelioğlu, Ferda; Durmuş, Mahmut; Kılıç, Adem; Yeşilot, Serkan

doi:10.1016/j.poly.2009.05.027

Cited by 45 publications

(14 citation statements)

References 29 publications

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“…1). The main industrial applications of a series of imidophosphates as phosphorus-nitrogen compounds are flame retardants for organic materials [3–9] and solubilizers for medicine [10–14]. The clarification of the protonation equilibria and the estimation of the basicities of the imidophosphates will be useful, since the hydrolysis reactions of the imidophosphates play important parts in these industrial applications.…”

Section: Introductionmentioning

confidence: 99%

Intrinsic 31P NMR Chemical Shifts and the Basicities of Phosphate Groups in a Short-Chain Imino Polyphosphate

2013

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The stepwise protonation constants of two linear triphosphate ligand anions, triphosphate, and di-imidotriphosphate, , were investigated by potentiometric titration, and the intrinsic chemical shifts of the stepwise protonated species of these anions were determined from the pH-dependence of the 31P NMR chemical shifts. All stepwise protonation constants of were found to be larger than those of , and the 31P NMR signals due to P3O8(NH)2 always appeared at a lower magnetic field compared to the signals due to P3O10. These results indicate higher basicity of the P3O8(NH)2 ligand, because it contains two imino groups in the ligand molecule. The 31P NMR signals for the end phosphate groups appear at a lower magnetic field than those for the middle phosphate groups, indicating that the basicity of the end phosphate group is higher than that of the middle phosphate group. It can be expected that the high basicity of the P3O8(NH)2 ligand brings about the formation of high stability complexes with various metal ions. Furthermore, the only 31P NMR signal due to the middle phosphate group of P3O8(NH)2 ligand molecule clearly showed a low-field shift in the range of pH < 2.5. The reason for this peculiar low-field shift should be the change of the localization of imino protons around the nitrogen atom in P3O8(NH)2.Graphical Abstract

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Section: Introductionmentioning

confidence: 99%

Intrinsic 31P NMR Chemical Shifts and the Basicities of Phosphate Groups in a Short-Chain Imino Polyphosphate

2013

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“…In recent years, a series of imidophosphates have been applied to the fields of the flame retardants for various organic materials [29][30][31][32][33][34][35] and the phosphorylation agents for various polysaccharides and biochemical compounds. [36][37][38][39][40] However, the chemical stabilities of the imidophosphates are not so high because of the nucleophilic attack from water molecules by the coexistence of metal ions; thus, the complexation behavior of various imidopolyphosphate anions is quite important.…”

Section: Introductionmentioning

confidence: 99%

⁹Be and ³¹P NMR analyses on the influence of imino groups on Be²⁺ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions

Maki

Tsujito

Nariai

et al. 2013

Magnetic Reson in Chemistry

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The complexation behaviors of Be²⁺ with cyclo-μ-imido triphosphate anions, cP₃O₉-n(NH)n(3-)n= 1, 2),have been investigated by both ⁹Be and ³¹P NMR techniques at -2.3 °C in order to clarify the coordination structures of the complexes. The spectra showed that cP₃O₉n(NH)n (n = 1, 2) ligands form ML, ML₂, and M₂L complexes with Be²⁺ ions, and the formation of complexes coordinating with nitrogen atoms of the cyclic framework in the ligand molecule has been excluded. These complexation trends are very similar to those of Be²⁺-cP₃O₆(NH)⁻³₃system, which has been reported by us. The peak deconvolution of ⁹BeNMR spectra made these beryllium complexes amenable to stability constant determinations. The stability constants of the complexes increase with an increase in the protonation constants of the ligands as the number of imino groups, which constitute the ligand molecules, is ascended. This increase is primarily attributable to the lower electronegativity of nitrogen atoms than oxygen atoms, which are directly bonded to central phosphorus atoms; moreover, tautomerism equilibrium in the entire of the imidopolyphosphate molecule is also responsible to the higher basicity. ³¹P NMR spectra measured concurrently have verified the formation of the complexes estimated by the ⁹Be NMR measurement. Intrinsic ³¹P NMR chemical shift values of the phosphorus atoms belonging to ligand molecules complexed with Be²⁺ cations have been determined. Not only the protonation constants but also the stability constants of all Be²⁺ complexes increase approximately linearly with an increase in the number of imino groups.

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“…3 However, the reactions carried out with di-, tri-and multi-functional reagents give different geometrical and optical isomers, e.g., spiro-, ansa-, dispiro-, trispiro, ansa-spiro and bino-architectures. [2][3][4] In addition, trimer and tetramer are also used as building blocks for dendrimers 5 and phosphazene polymers. 6 In recent years, the coordination complexes of the aminocyclophosphazene have attracted interest as an active research area.…”

Section: Introductionmentioning

confidence: 99%

Phosphorus–nitrogen compounds. Part 41. Ferrocenyl pendant-armed spirocyclopiperidinocyclotriphosphazatrienes: Langmuir–Blodgett thin films and biological activity studies

et al. 2018

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The Cl replacement reactions of N/N or N/O spirocyclic monoferrocenylcyclotriphosphazatrienes (1-5) with the piperidine resulted in the geminal-(6-10) and tetra-piperidinophosphazenes with monoferrocenyl pendant arm (11-15). The structures of all the new compounds were determined using spectroscopic techniques. The ultrathin Langmuir-Blodgett (LB) films of two compounds (3 and 12) were prepared. The characterization of the LB films using p-polarized grazing angle (GAIR) and horizontal attenuated total reflectance (HATR) techniques was carried out. The molecular and crystal structure of the compound 6 was examined using X-ray crystallography. In addition, the interactions between six compounds (6, 7, 11, 12, 14 and 15) and pBR322 plasmid DNA were investigated by agarose gel electrophoresis.

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The synthesis, thermal and photophysical properties of phenoxycyclotriphosphazenyl-substituted cyclic and polymeric phosphazenes

Cited by 45 publications

References 29 publications

Intrinsic 31P NMR Chemical Shifts and the Basicities of Phosphate Groups in a Short-Chain Imino Polyphosphate

Intrinsic 31P NMR Chemical Shifts and the Basicities of Phosphate Groups in a Short-Chain Imino Polyphosphate

⁹Be and ³¹P NMR analyses on the influence of imino groups on Be²⁺ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions

Phosphorus–nitrogen compounds. Part 41. Ferrocenyl pendant-armed spirocyclopiperidinocyclotriphosphazatrienes: Langmuir–Blodgett thin films and biological activity studies

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The synthesis, thermal and photophysical properties of phenoxycyclotriphosphazenyl-substituted cyclic and polymeric phosphazenes

Cited by 45 publications

References 29 publications

Intrinsic 31P NMR Chemical Shifts and the Basicities of Phosphate Groups in a Short-Chain Imino Polyphosphate

Intrinsic 31P NMR Chemical Shifts and the Basicities of Phosphate Groups in a Short-Chain Imino Polyphosphate

9Be and 31P NMR analyses on the influence of imino groups on Be2+ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions

Phosphorus–nitrogen compounds. Part 41. Ferrocenyl pendant-armed spirocyclopiperidinocyclotriphosphazatrienes: Langmuir–Blodgett thin films and biological activity studies

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⁹Be and ³¹P NMR analyses on the influence of imino groups on Be²⁺ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions