From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd<sup>II</sup>using<sup>113</sup>Cd solid-state NMR

Frost, Jamie M.; Kobera, Libor; Pialat, Amélie; Zhang, Yixin; Southern, Scott A.; Gabidullin, Bulat; Bryce, David L.; Murugesu, Muralee

doi:10.1039/c6cc04940k

Cited by 19 publications

(18 citation statements)

References 25 publications

(29 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…3 and Figure S7). [37][38][39][40] The appearance of multiple peaks likely occurs because some of the Cd(OA)2 may partially dissolve in the TCE TEKPol solution used for impregnation. S2).…”

Section: Introductionmentioning

confidence: 99%

“…For 5Cd-InP MSC no113 Cd CP-CPMG NMR signal was observed, likely due to the lower Cd concentration in the sample. A113 Cd chemical shift of -640 ppm indicates that the Cd atoms are coordinated by oxygen atoms [37][38][39][40]. Therefore, the isotropic113 Cd chemical shift suggests two probable locations for the Cd 2+ ions: (i) they are bound to both surface phosphate groups and OA However, it is also possible that Cd atoms within the MSC may be further from the 1 H spins of the ligands, resulting in less effective 1 H→ 113 Cd CP transfers.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy

et al. 2021

View full text Add to dashboard Cite

Indium phosphide quantum dots (InP QD) are a promising alternative to traditional QD materials that contain toxic heavy elements such as lead and cadmium. However, InP QD obtained from colloidal synthesis are often plagued by poor photoluminescence quantum yields (PL-QYs). In order to improve the PL-QY of InP QD, a number of post-synthetic treatments have been devised. Recently, it has been shown that InP post-synthetically treated with Lewis acid metal divalent cations (M-InP) exhibit enhanced PL-QY; however, the molecular structure and mechanism behind the improved PL-QY are not fully understood. To determine the surface structure of M-InP QD, dynamic nuclear polarization surface-enhanced nuclear magnetic resonance spectroscopy (DNP SENS) experiments were employed on a series of InP magic size clusters treated with Cd ions, InP QD, cadmium phosphide (Cd3P2) QD, and Cd-treated InP QD (Cd-InP QD). With the use of DNP SENS, we were able to obtain the 1D 31P and 113Cd NMR spectra, 113Cd{31P} rotational-echo double-resonance (REDOR) NMR spectra, and 31P{113Cd} dipolar heteronuclear multiple quantum correlation (D-HMQC) sequence. Changes in the phosphide 31P chemical shifts after Cd treatment provide indirect evidence that some Cd alloys into the sub-surface regions of the particle. DNPenhanced 113Cd solid-state NMR spectra suggest that most Cd ions are coordinated by oxygen atoms from either carboxylate ligands or surface phosphate groups. 113Cd{31P} REDOR and 31P{113Cd} D-HMQC experiments confirm that a subset of Cd ions are located on the surface of Cd-InP QD and coordinated with phosphate groups.

show abstract

“…3 and Figure S7). [37][38][39][40] The appearance of multiple peaks likely occurs because some of the Cd(OA)2 may partially dissolve in the TCE TEKPol solution used for impregnation. S2).…”

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy

et al. 2021

View full text Add to dashboard Cite

show abstract

“…There have been many recent reports that include the use of metal SSNMR to characterize MOFs . Although metal centers are ubiquitous within MOFs and should serve as a convenient spectroscopic handle for SSNMR characterization, many MOFs feature multiple non‐equivalent metal sites that reside in similar chemical environments, which give rise to overlapping signals and pose a severe obstacle to metal SSNMR characterization.…”

Section: Resultsmentioning

confidence: 99%

Complete multinuclear solid‐state NMR of metal‐organic frameworks: The case of α‐Mg‐formate

Zhang

Huang

2016

Concepts Magnetic Resonance

View full text Add to dashboard Cite

Metal-organic frameworks (MOFs) are exciting porous materials with a growing number of applications ranging from catalysis to gas storage. Establishing logical connections between the local MOF structure and its properties is not often straightforward, however, solid-state NMR is a sensitive probe of local structure and can be used to shed light on processes such as guest adsorption and gas motion within MOFs. As illustrated using our recent works on the microporous a-Mg-formate (Mg 3 (HCOO) 6 ) MOF, complete multinuclear solid-state NMR characterization of MOFs is now possible, and can provide unique insight that is not readily available through other methods. A wide variety of solid-state NMR techniques have been employed, including direct-excitation, cross-polarization, fast magic-angle spinning, and two-dimensional experiments. New variable-temperature 2 H solid-state NMR data of deuterated hydrogen gas within a-Mg-formate and the resulting detailed dynamic information is also presented, analyzed, and discussed.

show abstract

“…By switching from discrete metal complex structures to extended ones, such as 1D, 2D or 3D coordination polymers, some properties can be altered, in the sense of either diminishing or enhancing some (e.g. photophysical or thermal) or even the appearance of new features (e.g., porosity) . In addition, by translating to infinite crystalline solid architectures, spaces are created that make it possible to access metal‐based entities through which structures can be further controlled and transformed.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, by translating to infinite crystalline solid architectures, spaces are created that make it possible to access metal‐based entities through which structures can be further controlled and transformed. [2b] However, the rational design and synthesis of the extended structures remains a great challenge due to the multitude of factors that compete in the assembly of the final complex: metal nature, pH, temperature, solvents and obviously ligands . As a result, the design and preparation of coordination polymers as well as the investigation of their applicative potential is an active research field .…”

Section: Introductionmentioning

confidence: 99%

Nanoscale Coordination Polymer of Dimanganese(II) as Infinite, Flexible Nanosheets with Photo‐Switchable Morphology

Shova¹,

Vlad²,

Damoc³

et al. 2020

Eur J Inorg Chem

View full text Add to dashboard Cite

An original co‐ligand association, consisting of 4,4'‐azopyridine and 1,3‐bis(carboxypropyl)tetramethyldisiloxane, is used for complexing MnII, to obtain a 2D dinuclear coordination array having infinite horizontal dimensions and nanometric thickness. Due to the shielding effect of the tetramethyldisiloxane units facing outwards on both sides, the sheets are free of any chemical or physical intermolecular interactions, as crystallographic analysis reveals. The compound shows two glass transitions, at –51 and 33 °C, and begins to decompose at 292 °C. The co‐existence in the structure of the highly hydrophobic tetramethyldisiloxane spacers and the polar metal complexed units confers amphiphilic character to the compound, making it capable of reducing the surface tension of the DMF, from 35.8 to 29.4 mN/m, at a critical micellar concentration around 1 wt.‐% complex. The presence of aggregates in solution is evidenced by dynamic light scattering. The light sensitive azopyridine units make the compound photo‐responsive. This behavior occurs both in solution as well as in the film, where the compound self‐assembles in micellar morphology when UV‐irradiated. Both conductivity and dielectric permittivity of the film increase as a result of trans–cis configuration. Magnetic measurement data indicate two antiferromagnetic coupled spins, S = 5/2, that are able to interact with small external magnetic field, i.e., during MFM scanning.

show abstract

From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd^IIusing¹¹³Cd solid-state NMR

Cited by 19 publications

References 25 publications

Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy

Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy

Complete multinuclear solid‐state NMR of metal‐organic frameworks: The case of α‐Mg‐formate

Nanoscale Coordination Polymer of Dimanganese(II) as Infinite, Flexible Nanosheets with Photo‐Switchable Morphology

Contact Info

Product

Resources

About

From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of CdIIusing113Cd solid-state NMR

Cited by 19 publications

References 25 publications

Elucidating the Location of Cd2+ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization 31P and 113Cd Solid-State NMR Spectroscopy

Elucidating the Location of Cd2+ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization 31P and 113Cd Solid-State NMR Spectroscopy

Complete multinuclear solid‐state NMR of metal‐organic frameworks: The case of α‐Mg‐formate

Nanoscale Coordination Polymer of Dimanganese(II) as Infinite, Flexible Nanosheets with Photo‐Switchable Morphology

Contact Info

Product

Resources

About

From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd^IIusing¹¹³Cd solid-state NMR

Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy

Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy