A Smart Phosphine–Diyne Polymer Displays “Turn-On” Emission with a High Selectivity for Gold(I/III) Ions

Mackenzie, Harvey Kyle; Rawe, Benjamin W.; Samedov, Kerim; Walsgrove, Henry T G; Uva, Azalea; Han, Zeyu; Gates, Derek P.

doi:10.1021/jacs.0c04330

Cited by 22 publications

(14 citation statements)

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“…DFT calculations have proven to be an indispensable tool for the detailed analysis and prediction of the electronical and optical properties of phosphole systems and their tuning via the substitution pattern. ,,,− Therefore, the impact of the functional silyl groups in the novel phospholes 1 – 6 on the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energies is of great interest because the latter determines the photophysical properties in the UV/vis region. To explore the electronic influence of the silyl units, DFT calculations at the B3LYP/6-311+G(d,p) level of theory have been carried out.…”

Section: Results and Discussionmentioning

confidence: 99%

Trifunctional Silyl Groups as Anchoring Units in the Preparation of Luminescent Phosphole–Silica Hybrids

et al. 2021

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A synthetic strategy to β-silylphospholes with three methoxy, ethoxy, chloro, hydrido, or phenyl substituents at silicon has been developed, starting from trimethoxy, triethoxy, or triphenyl silyl substituted phenyl phosphanides and 1,4-diphenyl-1,3-butadiyne. These trifunctional silylphospholes were attached to the surface of uniform spheric silica particles (15 μm) and, for comparison, to a polyhedral silsesquioxane (POSS)–trisilanol as a molecular model to explore their luminescent properties in comparison with the free phospholes. Density functional theory calculations were performed to investigate any electronic perturbation of the phosphole system by the trifunctional silyl anchoring unit. For the immobilized phospholes, cross-polarization magic-angle-spinning NMR measurements (13C, 29Si, and 31P) were carried out to explore the bonding situation to the silica surface. Thermogravimetric analysis and X-ray photoelectron spectroscopy measurements were performed to approximate the amount of phospholes covering the silica surface. Identity and purity of all novel phospholes have been established with standard techniques (multinuclear NMR, mass spectrometry, and elemental analysis) and X-ray diffraction for the POSS derivative.

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Section: Results and Discussionmentioning

confidence: 99%

Trifunctional Silyl Groups as Anchoring Units in the Preparation of Luminescent Phosphole–Silica Hybrids

et al. 2021

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“…13 C{ 1 H} NMR (100.6 MHz): δ = 33. 3, 33.2, 32.0, 31.5, 30.9, 30.8, 29.8, 29.6, 29.5, 29.4, 28.9, 28.4, 28.3, 26.8, 26.6, 21.1, 21.0, 14.0, 13.9 ppm; 31 P NMR (161.8 MHz): δ = À137.7 (t, 1 J PH = 186.1 Hz; RPH 2 ), À68.7 (d, 1 J PH = 194.2 Hz; R 2 PH), À31.5 (s; PR 3 ) ppm; FT-IR (ranked intensity): ν = 2918 (1), 2850 (2), 2280 (3; ν PH ), 1464 (4), 1418 (7), 1349 (12), 1342 (13), 1296 (15), 1197 (14), 1079 (6), 992 (10), 836 (8), 812 (9), 720 (5), 634 (11) cm À1 ; decomposition onset = 160 C; Char yield = 0%; broad endotherm centered at 0 C (Figure S15).…”

Section: Compoundmentioning

confidence: 99%

“…The reaction mixture was heated to 60 C in a stainlesssteel pressure reactor for 18 h followed by removal of volatiles in vacuo to give a colorless oil. 13 (7), 1414 (8), 1343 (10), 1295 (15), 999 (12), 808 (13), 768 (9), 721 (5), 710 (6), 657 (14), 464 (11) cm À1 ; decomposition onset = 201 C; Char yield = 0%; T g onset = À92 C. Network 3 was oxidized using excess hydrogen peroxide (20 wt% in water), extracted with CH 2 Cl 2 and dried in vacuo to give a colorless oil that was analyzed by GPC and MALDI-TOF-MS, using DCTB as the matrix.…”

Section: Compoundmentioning

confidence: 99%

“…[1,2] For example, functionalizing the non-bonding pair of electrons on trivalent phosphorus centers has been adopted by polymer chemists taking the lead from small molecule systems to tune electrochemical and optical properties. [3][4][5][6][7][8][9][10][11][12] Meanwhile, examples where post-polymerization functionalization of trivalent phosphorus-containing polymers leads to advantages that are unique to macromolecular over molecular systems include polymers that can scavenge homogenous catalysts [13,14] and an ability to tune the shapes and sizes of self-assembled nanostructures. [15] There remains a slew of sophisticated p block reactions that take place with molecular phosphines, which have yet to be translated to a macromolecular context, [16] leaving an area of untapped potential in material exploration and development.…”

Section: Introductionmentioning

confidence: 99%

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Polymer networks functionalized with low‐valent phosphorus cations

Béland

Wang

Sham

et al. 2022

Journal of Polymer Science

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In this work, we show that polymer networks composed of tertiary alkyl phosphines can be cleanly functionalized with phosphino‐phosphonium or triphosphenium cations. Methods for functionalizing the polymers range from halide abstraction of commercially available reagents, to ligand exchange from simple to make reported compounds, and finally, macromolecular ligand design guided by observations made at the molecular level to accommodate the formation of kinetically favored triphosphenium cation functionalized networks. The synthesis, comprehensive characterization, and comparison of the new polymers to molecular analogues is outlined. It is shown the addition of the low valent phosphorus centers to the polymer network has the effect of tuning material physical properties.

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“…Due to the high cost, complexity, and time consumption in conventional methods, fluorescence detection has become the most widespread method for Au(III) detection due to its high sensitivity and facile operation. , Many Au(III) fluorescent probes with limits of detection (LOD) as low as ppb level have been designed and developed from the reaction or coordination sensing mechanism. − From the viewpoint of Au(III) recovery, adsorptive capture is the most common method due to its low cost, simplicity, and high efficiency. Numerous Au(III) adsorbents have been presented with a maximum adsorption capacity of up to 3257.3 mg/g. − However, most reports focus on one aspect, that is, detection or recovery of Au(III).…”

Section: Introductionmentioning

confidence: 99%

An Imidazole Thione-Modified Polyhedral Oligomeric Silsesquioxane for Selective Detection and Adsorptive Recovery of Au(III) from Aqueous Solutions

Chen

Wang

Feng

et al. 2021

ACS Appl. Mater. Interfaces

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Developing a material toward simultaneous detection and recovery of gold ions (Au(III)) is highly desirable for the economy and the environment. Herein, we report a highly efficient dual-function material for simultaneous Au(III) detection and recovery by simply introducing abundant imidazole thione and thioether groups in one system. This material, that is, an imidazole thione-modified polyhedral oligomeric silsesquioxane (POSS-2), was prepared by a mild reaction of an imidazolium-containing POSS and sulfur at ambient temperature. The POSS-2 suspension in water can rapidly and selectively detect Au(III) with a very low limit of detection of 1.2 ppb by fluorescence quenching or a visualized color change from white to dark orange. POSS-2 can also selectively and efficiently capture Au(III) with a maximum adsorption uptake of 1486.5 mg/g. The adsorption process well fits with the pseudo-second-order kinetic and Langmuir models. The intriguing dual-function performance is better than most of the previous Au(III) probes or adsorbents. The mechanism study reveals that the detection and adsorption behavior are mainly caused by the redox reaction and coordination between imidazole thione and thioether groups and Au(III). Furthermore, POSS-2 was successfully utilized to extract gold without interference from a discard CPU. These results indicate the potential application of the present dual-function material for Au(III) detection and recovery from aqueous solutions. More dual-functional materials could be designed and prepared by this simple strategy.

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A Smart Phosphine–Diyne Polymer Displays “Turn-On” Emission with a High Selectivity for Gold(I/III) Ions

Cited by 22 publications

References 85 publications

Trifunctional Silyl Groups as Anchoring Units in the Preparation of Luminescent Phosphole–Silica Hybrids

Trifunctional Silyl Groups as Anchoring Units in the Preparation of Luminescent Phosphole–Silica Hybrids

Polymer networks functionalized with low‐valent phosphorus cations

An Imidazole Thione-Modified Polyhedral Oligomeric Silsesquioxane for Selective Detection and Adsorptive Recovery of Au(III) from Aqueous Solutions

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