The Relationship between <sup>207</sup>Pb NMR Chemical Shift and Solid-State Structure in Pb(II) Compounds

Dmitrenko, Olga; Bai, Shi; Beckmann, Peter A.; Bramer, Scott Van; Vega, and Alexander J.; Dybowski, Cecil

doi:10.1021/jp711182z

Cited by 45 publications

(60 citation statements)

References 38 publications

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“…Figure 5 shows the near-octahedron. It is convenient to characterize the departure from a perfect octahedral arrangement by the angles  where the I-Pb-I angles are 90 O +  [32]. All values of  are 0 for a perfect octahedron.…”

Section: The Geometry Of the Near-octahedral Structure Of The [Pbi6] mentioning

confidence: 99%

A review of polytypism in lead iodide

Beckmann

2010

Cryst. Res. Technol.

106

109

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Key words lead iodide structure, layered inorganic structures, viewing different polytypes Lead Iodide (PbI2) is an important inorganic solid for both basic scientific research and possible technological applications and in this brief review we discuss the structure of PbI2. Although the basic structure is a simple I-Pb-I layered structure with a [PbI6] 4-near-octahedron being the basic building block, there are many ways of stacking the layers which results in many polytypes. We present 20 of the 23 entries for the structure of PbI2 from the Inorganic Structural Database and order them by polytype. This represents more than 80 years of crystallographic research in the structure of this compound. We present a simple way to view the 2H, 4H, 6H, and 6R polytypes and extend the procedure to higher-order polytypes. We note a relationship, not generally appreciated, between the distortion of the near [PbI6] 4-octahedrons and the polytype. We suggest that the significance of vacancies has only recently been appreciated. We suggest that small discrepancies in structure determination are probably due to different distributions of vacancies and that there are, in practice, very many structures for macroscopic or even mesoscopic samples of a given polytype when vacancies are considered.

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Section: The Geometry Of the Near-octahedral Structure Of The [Pbi6] mentioning

confidence: 99%

A review of polytypism in lead iodide

Beckmann

2010

Cryst. Res. Technol.

106

109

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“…[15] Of the four stable lead isotopes, only 207 Pb is NMR-active (I = 1 = 2 ), with a moderate resonance frequency (125.2 MHz at 14.1 T) and 22.1 % natural abundance. [19] 207 Pb has one of the largest NMR chemical shift ranges (>15 000 ppm versus 13 C % 300 ppm) and is highly anisotropic, [20] displaying great sensitivity to changes in electron density; [21][22][23][24] these are ideal properties for determining the effect of lone-pair activity within lead(II) coordination polymers. The diagnostic NMR interaction is the chemical shift anisotropy (CSA), which describes the orientational dependence of chemical shielding, and is generally present if the symmetry is not cubic in origin.…”

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confidence: 99%

Characterising Lone‐Pair Activity of Lead(II) by ²⁰⁷Pb Solid‐State NMR Spectroscopy: Coordination Polymers of [N(CN)₂]⁻ and [Au(CN)₂]⁻ with Terpyridine Ancillary Ligands

Greer

Michaelis

Katz

et al. 2011

Chemistry A European J

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A series of lead(II) coordination polymers containing [N(CN)(2)](-) (DCA) or [Au(CN)(2)](-) bridging ligands and substituted terpyridine (terpy) ancillary ligands ([Pb(DCA)(2)] (1), [Pb(terpy)(DCA)(2)] (2), [Pb(terpy){Au(CN)(2)}(2)] (3), [Pb(4'-chloro-terpy){Au(CN)(2)}(2)] (4) and [Pb(4'-bromo-terpy)(μ-OH(2))(0.5){Au(CN)(2)}(2)] (5)) was spectroscopically examined by solid-state (207)Pb MAS NMR spectroscopy in order to characterise the structural and electronic changes associated with lead(II) lone-pair activity. Two new compounds, 2 and [Pb(4'-hydroxy-terpy){Au(CN)(2)}(2)] (6), were prepared and structurally characterised. The series displays contrasting coordination environments, bridging ligands with differing basicities and structural and electronic effects that occur with various substitutions on the terpyridine ligand (for the [Au(CN)(2)](-) polymers). (207)Pb NMR spectra show an increase in both isotropic chemical shift and span (Ω) with increasing ligand basicity (from δ(iso) = -3090 ppm and Ω = 389 ppm for 1 (the least basic) to δ(iso) = -1553 ppm and Ω = 2238 ppm for 3 (the most basic)). The trends observed in (207)Pb NMR data correlate with the coordination sphere anisotropy through comparison and quantification of the Pb-N bond lengths about the lead centre. Density functional theory calculations confirm that the more basic ligands result in greater p-orbital character and show a strong correlation to the (207)Pb NMR chemical shift parameters. Preliminary trends suggest that (207)Pb NMR chemical shift anisotropy relates to the measured birefringence, given the established correlations with structure and lone-pair activity.

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“…Chemical shifts were converted to temperatures using the well-established temperature dependence of lead nitrate of 0.758 ppmK À1 [28,39,40]. Hand-wound coils were made using either 25, 62 or 80 lm diameter insulated copper wire, consisting of 5 turns, and lengths of ca.…”

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confidence: 99%

Experimental and numerical examination of eddy (Foucault) currents in rotating micro-coils: Generation of heat and its impact on sample temperature

Aguiar

Jacquinot

Sakellariou

2009

Journal of Magnetic Resonance

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The Relationship between ²⁰⁷Pb NMR Chemical Shift and Solid-State Structure in Pb(II) Compounds

Cited by 45 publications

References 38 publications

A review of polytypism in lead iodide

A review of polytypism in lead iodide

Characterising Lone‐Pair Activity of Lead(II) by ²⁰⁷Pb Solid‐State NMR Spectroscopy: Coordination Polymers of [N(CN)₂]⁻ and [Au(CN)₂]⁻ with Terpyridine Ancillary Ligands

Experimental and numerical examination of eddy (Foucault) currents in rotating micro-coils: Generation of heat and its impact on sample temperature

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The Relationship between 207Pb NMR Chemical Shift and Solid-State Structure in Pb(II) Compounds

Cited by 45 publications

References 38 publications

A review of polytypism in lead iodide

A review of polytypism in lead iodide

Characterising Lone‐Pair Activity of Lead(II) by 207Pb Solid‐State NMR Spectroscopy: Coordination Polymers of [N(CN)2]− and [Au(CN)2]− with Terpyridine Ancillary Ligands

Experimental and numerical examination of eddy (Foucault) currents in rotating micro-coils: Generation of heat and its impact on sample temperature

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The Relationship between ²⁰⁷Pb NMR Chemical Shift and Solid-State Structure in Pb(II) Compounds

Characterising Lone‐Pair Activity of Lead(II) by ²⁰⁷Pb Solid‐State NMR Spectroscopy: Coordination Polymers of [N(CN)₂]⁻ and [Au(CN)₂]⁻ with Terpyridine Ancillary Ligands