An official website of the United States government
Pegmatites are shallow, coarse-grained magmatic intrusions with crystals occasionally approaching meters in length. Compared to their plutonic hosts, pegmatites are thought to have cooled rapidly, suggesting that these large crystals must have grown fast. Growth rates and conditions, however, remain poorly constrained. Here we investigate quartz crystals and their trace element compositions from miarolitic cavities in the Stewart pegmatite in southern California, USA, to quantify crystal growth rates. Trace element concentrations deviate considerably from equilibrium and are best explained by kinetic effects associated with rapid crystal growth. Kinetic crystal growth theory is used to show that crystals accelerated from an initial growth rate of 10−6–10−7 m s−1 to 10−5–10−4 m s−1 (10-100 mm day−1 to 1–10 m day−1), indicating meter sized crystals could have formed within days, if these rates are sustained throughout pegmatite formation. The rapid growth rates require that quartz crystals grew from thin (micron scale) chemical boundary layers at the fluid-crystal interfaces. A strong advective component is required to sustain such thin boundary layers. Turbulent conditions (high Reynolds number) in these miarolitic cavities are shown to exist during crystallization, suggesting that volatile exsolution, crystallization, and cavity generation occur together.
more »
« less
Molecular Crystal Microcapsules: Formation of Sealed Hollow Chambers via Surfactant‐Mediated Growth
Abstract Hollow organic molecular cocrystals comprised of 9‐methylanthracene‐1,2,4,5‐tetracyanobenzene (9MA‐TCNB) and naphthalene‐1,2,4,5‐tetracyanobenzene (NAPH‐TCNB) were fabricated using a surfactant‐mediated co‐reprecipitation method. The crystals exhibit a narrow size distribution that can be easily tuned by varying the concentration of surfactant and incubation temperature. The rectangular crystals possess symmetrical twinned cavities with an estimated storage volume on the order of 10−10 L. An aqueous dye solution can be incorporated into the cavities during crystal growth and stored inside for up to several hours, confirming the sealed nature of the hollow chambers. Our results demonstrate that it is possible to harness non‐classical crystal growth to fabricate organic molecular crystals with novel topologies.
more »
« less
- PAR ID:
- 10235905
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 59
- Issue:
- 51
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 23035-23039
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The incorporation of metal-organic frameworks into advanced devices remains a desirable goal, but progress is hindered by difficulties in preparing large crystalline metal-organic framework films with suitable electronic performance. We demonstrate the direct growth of large-area, high quality, and phase pure single metal-organic framework crystals through chemical vapor deposition of a dimolybdenum paddlewheel precursor, Mo2(INA)4. These exceptionally uniform, high quality crystals cover areas up to 8600 µm2and can be grown down to thicknesses of 30 nm. Moreover, scanning tunneling microscopy indicates that the Mo2(INA)4clusters assemble into a two-dimensional, single-layer framework. Devices are readily fabricated from single vapor-phase grown crystals and exhibit reversible 8-fold changes in conductivity upon illumination at modest powers. Moreover, we identify vapor-induced single crystal transitions that are reversible and responsible for 30-fold changes in conductivity of the metal-organic framework as monitored by in situ device measurements. Gas-phase methods, including chemical vapor deposition, show broader promise for the preparation of high-quality molecular frameworks, and may enable their integration into devices, including detectors and actuators.more » « less
-
Optically-active optoelectronic materials are of great interest for many applications, including chiral sensing and circularly polarized light emission. Traditionally, such applications have been enabled by synthetic strategies to design chiral organic semiconductors and conductors. Here, centrosymmetric tetrathiafulvalene (TTF) crystals are rendered chiral on the mesoscale by crystal twisting. During crystallization from the melt, helicoidal TTF fibers were observed to grow radially outwards from a nucleation centre as spherulites, twisting in concert about the growth direction. Because molecular crystals exhibit orientation-dependent refractive indices, periodic concentric bands associated with continually rotating crystal orientations were observed within the spherulites when imaged between crossed polarizers. Under certain conditions, concomitant crystal twisting and bending was observed, resulting in anomolous crystal optical behavior. X-ray diffraction measurements collected on different spherulite bands indicated no difference in the molecular packing between straight and twisted TTF crystals, as expected for microscopic twisting pitches between 20–200 μm. Mueller matrix imaging, however, revealed preferential absorption and refraction of left- or right-circularly polarized light in twisted crystals depending on the twist sense, either clockwise or counterclockwise, about the growth direction. Furthermore, hole mobilities of 2.0 ± 0.9 × 10 −6 cm 2 V −1 s −1 and 1.9 ± 0.8 × 10 −5 cm 2 V −1 s −1 were measured for straight and twisted TTF crystals deposited on organic field-effect transistor platforms, respectively, demonstrating that crystal twisting does not negatively impact charge transport in these systems.more » « less
-
Abstract Solid‐state packing plays a defining role in the properties of a molecular organic material, but it is difficult to elucidate in the absence of single crystals that are suitable for X‐ray diffraction. Herein, we demonstrate the coupling of divergent synthesis with microcrystal electron diffraction (MicroED) for rapid assessment of solid‐state packing motifs, using a class of chiral nanocarbons—expanded helicenes—as a proof of concept. Two highly selective oxidative dearomatizations of a readily accessible helicene provided a divergent route to four electron‐deficient analogues containing quinone or quinoxaline units. Crystallization efforts consistently yielded microcrystals that were unsuitable for single‐crystal X‐ray diffraction, but ideal for MicroED. This technique facilitated the elucidation of solid‐state structures of all five compounds with <1.1 Å resolution. The otherwise‐inaccessible data revealed a range of notable packing behaviors, including four different space groups, homochirality in a crystal for a helicene with an extremely low enantiomerization barrier, and nanometer scale cavities.more » « less
-
Abstract Phase transitions are typically quantified using order parameters, such as crystal lattice distances and radial distribution functions, which can identify subtle changes in crystalline materials or high‐contrast phases with large structural differences. However, the identification of phases with high complexity, multiscale organization and of complex patterns during the structural fluctuations preceding phase transitions, which are essential for understanding the system pathways between phases, is challenging for those traditional analyses. Here, it is shown that for two model systems— thermotropic liquid crystals and a lyotropic water/surfactant mixtures—graph theoretical (GT) descriptors can successfully identify complex phases combining molecular and nanoscale levels of organization that are hard to characterize with traditional methodologies. Furthermore, the GT descriptors also reveal the pathways between the different phases. Specifically, centrality parameters and node‐based fractal dimension quantify the system behavior preceding the transitions, capturing fluctuation‐induced breakup of aggregates and their long‐range cooperative interactions. GT parameterization can be generalized for a wide range of chemical systems and be instrumental for the growth mechanisms of complex nanostructures.more » « less
