Triboluminescence-structure relationships in polymorphs of hexaphenylcarbodiphosphorane and anthranilic acid, molecular crystals, and salts

Hardy, Gordon E.; Kaska, William C.; Chandra, B. P.; Zink, Jeffrey I.

doi:10.1021/ja00395a014

Cited by 159 publications

(87 citation statements)

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“…In the case of the diphosphaallenes, charge transfers from a lone pair of one phosphorus atom to a σ antibonding orbital localized on the C-P bond involving the other phosphorus are present, these interactions forcing the P-C-P angle to narrow. This type of interaction is also present for the discussed derivative IV.5 between the lone pair of the λ 3 σ 2 P and an antibonding orbital of σ symmetry on λ 5 σ 3 P-C; the orbitals involved are represented in The data of Table 2 show that the P-C-P angle is as expected highly dependent on the nature of the substituents on the phosphorus atom and of its hybridization [13][14][15][16][17][18]. A very strained angle of 115.05º has been reported for i-Pr 2 NP=C=PPh 2 Ni-Pr 2 [16], a derivative containing dicoordinated trivalent and tetracoordinated pentavalent phosphorus atoms in the PCP backbone.…”

Section: Resultssupporting

confidence: 53%

Theoretical study of structural patterns in CH2OP2 isomers

et al. 2010

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DFT calculations have been performed on the derivatives of formula CH 2 OP 2 to determine their total energy, the relative energy between the isomers and their geometry. Among compounds with a P-C-P linkage, the most stable one is the 2-hydroxy-1,2-diphosphirene II.1, a threemembered heterocycle with a P=C unsaturation. The phosphavinylidene(oxo)phosphorane HP=C=P(O)H IV.5 (which has the same skeleton as the experimentally obtained Mes*P=C=P(O)Mes*) lies 36.30 kcal mol -1 above it. The least stable compounds are carbenes; the singlet carbenes are more stable than the triplet ones.

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Section: Resultssupporting

confidence: 53%

Theoretical study of structural patterns in CH2OP2 isomers

et al. 2010

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“…At the present time it would be most difficult to make an estimate of the electronic excitation expected in a clay mineral from some specified application of mechanical stress. Unlike the case of radioactive bombardment, therd exists only the beginnings of either a theoretical, or an empirical (Linet al, 1980;Hardy et al, 1977;Hardy et al, 1981), framework within which mechanical forces can be translated into equivalent excitation. However, the evidence for electronic excitation resulting from mechanical stress is well documented in a variety of systems.…”

Section: Ivb Penetrating Energy Sourcesmentioning

confidence: 99%

A possible energetic role of mineral surfaces in chemical evolution

Coyne

1985

Origins Life Evol Biosphere

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The postulated roles of clays and other minerals in chemical evolution and the origin of life are reconsidered in terms of the interaction of these minerals with penetrating sources of energy such as ionizing radiation and mechanical stress. This interaction, including such facets as excitation, degradation, storage, and transfer, is considered here with regard to its profound potential for altering the capabilities of minerals to serve both as substrates for prebiological chemistry and as inorganic prototypic life forms. The interaction of minerals and energy in relationship to surface chemistry is discussed in terms of the spectroscopic properties of minerals, the interaction of energy with condensed phases, some commonly accepted concepts of heterogeneous catalysis in the absence of electronic energy inputs, and some commonly accepted and novel means by which surface activity might be enhanced in the presence of energy inputs. An estimation is made of the potential contribution of two poorly characterized prebiotic energy sources, natural radioactive decay and triboelectric energy. These estimates place a conservative lower limit on their prebiotic abundance. Also some special properties of these energy sources, relative to solar energy, are pointed out which might give them particular suitability for driving reactions occurring under geological conditions. Skeletal support for this broadly defined framework of demonstrated and potential relationships between minerals, electronic excitation, and surface reactivity, as applied to chemical evolution, is provided from the results of our studies on 1/1 clays. We have discovered and partially characterized a number of novel luminescent properties of these clays, that indicate energy storage and transfer processes in clays. These luminescent properties are interpreted in relationship to the electron spin resonance phenomena, to provide a basis for estimating the potential significance of energy storage and transduction in monitoring or driving clay surface chemistry. Consideration of the electronic structure of abundant minerals in terms of band theory and localized defect centers provides a predictive theoretical framework from which to rationalize the capacity of these materials to store and transduce energy. The bulk crystal is seen as a collecting antenna for electronic energy, with the defect centers serving as storage sites. The clay properties produced by isomorphic substitution appear to be intimately associated with all of the life-mimetic chemical processes that have been attributed to clays.(ABSTRACT TRUNCATED AT 400 WORDS)

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“…Many crystals are known to give emission of electromagnetic radiation, electrons, ions, and photons during fracture and some of them can emit light even during their deformation [19,20]. However, the radiation intensity in most of the materials is too weak and difficult to detect.…”

Section: Introductionmentioning

confidence: 99%