Crystals of the 2,4,6-tri-tert-butylphenoxyl radical have been isolated and characterized by X-ray diffraction, and calculations have been performed that give the distribution of spin density in the radical.
Crystals grow in the mind's eye by the addition of small units to a monolith each part of which is in fixed translational relation to every other part. Here, it is shown that growth can induce reversible twisting and untwisting of macroscopic crystals of hippuric acid (N-benzoylglycine, C(9)H(9)NO(3)) on the scale of radians. Crystals growing in undercooled melts of hippuric acid twist about the axis of elongation. At the same time the twisting is undone by new elastic stresses that build up as the crystal thickens. The dynamic interplay of twisting and untwisting ultimately fixes the crystal morphology. A correspondence between the optical properties of hippuric acid single crystals and twisted needles measured with a Mueller matrix microscope is established. The measured crystalloptical properties are in complete accord with the optical indicatrix rotating helically along the axis of elongation at the growth front, or counter-rotating so as to unwind earlier growth. The reversible morphological changes captured here in situ are likely also found in banded spherulites of high molecular weight polymers, optically modulated chalcedony minerals, elements, proteins, and other molecular crystals for which there is evidence of helical twisting. The analysis of such systems is usually predicated on the relationship of crystalline helical pitch to a power law exponent. However, in the absence of previous considerations of untwisting, the mechanistic content of such relationships is questionable.
A spectroscopic Mueller matrix polarimeter with four photoelastic modulators (PEMs) and no moving parts is introduced. In the 4-PEM polarimeter, all the elements of the Mueller matrix are simultaneously determined from the analysis of the frequencies of the time-dependent intensity of the light beam.
D-Mannitol belongs to a large and growing family of crystals with helical morphologies (Yu, L. J. Am. Chem. Soc.2003, 125, 6380). Two polymorphs of D-mannitol, α and δ, when grown in the presence of additives such as poly(vinylpyrrolidone) (PVP) or D-sorbitol, form ring-banded spherulites composed of handed helical fibrils, where the helix axes correspond to the radial growth directions. The two polymorphs form helices with opposite senses in the presence of PVP but the same sense in the presence of D-sorbitol. The characteristic dimensions of the fibrils, including thickness, aspect ratio, and pitch, were determined by scanning probe and electron microscopies. These values must form the basis of any theory that presupposes what forces give rise to crystal twisting, a problem that has been broached but unsettled in the literature of polymer crystallization. The interdependence of the rhythmic variations of both linear and circular birefringence, as determined by Mueller matrix microscopy, informs the cooperative organization of mannitol fibers. The microstructure of mannitol ring-banded spherulites compares favorably to that of high polymers and is evaluated within the context of current theories of crystal twisting.
Ferdinand Bernauer proposed in his monograph, "Gedrillte" Kristalle (1929), that a great number of simple, crystalline substances grow from solution or from the melt as polycrystalline spherulites with helically twisting radii that give rise to distinct bull's-eye patterns of concentric optical bands between crossed polarizers. The idea that many common molecular crystals can be induced to grow as mesoscale helices is a remarkable proposition poorly grounded in theories of polycrystalline pattern formation. Recent reinvestigation of one of the systems Bernauer described revealed that rhythmic precipitation in the absence of helical twisting accounted for modulated optical properties [Gunn, E. et al. J. Am. Chem. Soc. 2006, 128, 14234-14235]. Herein, the Bernauer hypothesis is re-examined in detail for three substances described in "Gedrillte" Kristalle, potassium dichromate, hippuric acid, and tetraphenyl lead, using contemporary methods of analysis not available to Bernauer, including micro-focus X-ray diffraction, electron microscopy, and Mueller matrix imaging polarimetry. Potassium dichromate is shown to fall in the class of rhythmic precipitates of undistorted crystallites, while hippuric acid spherulites are well described as helical fibrils. Tetraphenyl lead spherulites grow by twisting and rhythmic precipitation. The behavior of tetraphenyl lead is likely typical of many substances in "Gedrillte" Kristalle. Rhythmic precipitation and helical twisting often coexist, complicating optical analyses and presenting Bernauer with difficulties in the characterization and classification of the objects of his interest.
It is well-known that circular dichroism (CD) measurements of anisotropic media may contain artifacts that result from mixed linear anisotropies. Such artifacts are generally considered a nuisance. However, systematic artifacts, carefully measured, may contain valuable information. Herein, polycrystalline spherulites of D-sorbitol grown from the melt were analyzed with a Mueller matrix microscope, among other differential polarization images devices. As spherulites grew into one another they developed strong apparent optical rotation and CD signals at the boundaries between spherulites. These signals are shown not to have a chiroptical origin but rather result from the interactions of linear anisotropies in polycrystalline bodies. Such chiroptical artifacts should not be dismissed reflexively. Rather, they are comprehensible crystal-optical effects that serve to define mesoscale structure.
Crystal optical properties of banded spherulites of 21 different compounds--molecular crystals, polymers, and minerals--with helically twisted fibers were analyzed with Mueller matrix polarimetry. The well-established radial oscillations in linear birefringence of many polycrystalline ensembles is accompanied by oscillations in circular birefringence that cannot be explained by the natural optical activity of corresponding compounds, some of which are centrosymmetric in the crystalline state. The circular birefringence is shown to be a consequence of misoriented, overlapping anisotropic lamellae, a kind of optical activity associated with the mesoscale stereochemistry of the refracting components. Lamellae splay as a consequence of space constraints related to simultaneous twisting of anisometric lamellae. This mechanism is supported by quantitative simulations of circular birefringence arising from crystallite twisting and splaying under confinement.
[CpIrCl(2)](2) () and new CpIr(III)(L-L)X complexes (L-L = N-O or C-N chelating ligands; X = Cl, I, Me) have been prepared and their reactivity with two-electron chemical oxidants explored. Reaction of with PhI(OAc)(2) in wet solvents yields a new chloro-bridged dimer in which each of the Cp ligands has been singly acetoxylated to form [Cp(OAc)Ir(III)Cl(2)](2) () (Cp(OAc) = eta(5)-C(5)Me(4)CH(2)OAc). Complex and related carboxy- and alkoxy-functionalized Cp(OR) complexes can also be prepared from plus (PhIO)(n) and ROH. [Cp(OAc)Ir(III)Cl(2)](2) () and the methoxy analogue [Cp(OMe)Ir(III)Cl(2)](2) () have been structurally characterized. Treatment of [CpIrCl(2)](2) () with 2-phenylpyridine yields CpIr(III)(ppy)Cl () (ppy = cyclometallated 2-phenylpyridyl) which is readily converted to its iodide and methyl analogues CpIr(III)(ppy)I and CpIr(III)(ppy)Me (). CpIr(III) complexes were also prepared with N-O chelating ligands derived from anthranilic acid (2-aminobenzoic acid) and alpha-aminoisobutyric acid (H(2)NCMe(2)COOH), ligands chosen to be relatively oxidation resistant. These complexes and were reacted with potential two-electron oxidants including PhI(OAc)(2), hexachlorocyclohexadienone (C(6)Cl(6)O), N-fluoro-2,4,6-trimethylpyridinium (Me(3)pyF(+)), [Me(3)O]BF(4) and MeOTf (OTf = triflate, CF(3)SO(3)). Iridium(V) complexes were not observed or implicated in these reactions, despite the similarity of the potential products to known CpIr(V) species. The carbon electrophiles [Me(3)O]BF(4) and MeOTf appear to react preferentially at the N-O ligands, to give methyl esters in some cases. Overall, the results indicate that Cp is not inert under oxidizing conditions and is therefore not a good supporting ligand for oxidizing organometallic complexes.
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