Alignment of Organic Crystals under Nanoscale Confinement. Ha, J., Hamilton, B., D., Hillmyer, M., A., & Ward, M., D. CRYSTAL GROWTH & DESIGN, 12(9):4494-4504, AMER CHEMICAL SOC, 9, 2012. abstract bibtex Nanocrystals of alpha,omega-alkanedicarboxylic acids
(HO2C(CH2)(n-2)CO2H, n = 3-13, odd) grown in aligned nanometer-scale
cylindrical pores of nanoporous poly(cyclohexylethylene) monoliths
(p-PCHE) adopt preferred orientations relative to the pore direction.
X-ray diffraction reveals that nanocrystals of malonic acid (n = 3)
grown in 14, 30, and 40 nm diameter pores adopted two preferred mutually
perpendicular orientations simultaneously, each orientation coinciding
with the direction of hydrogen-bonded chains in the solid state.
Nanocrystals of glutaric acid (n = 5) embedded within 30 and 40 nm pores
adopted orientations with hydrogen-bonded chains coincident with the
pore direction, but the chains were perpendicular to the pore direction
in 14 nm pores. Pimelic acid (n = 7) nanocrystals were oriented with
their hydrogen-bonded chains parallel to the pore direction, but
nanocrystals of longer alkane dicarboxylic acids (n = 9, 11, or 13)
adopted orientations in which the their hydrogen-bonded chains
progressively tilted away from the pore direction as the alkane length
was increased. This behavior can be attributed to increasingly strong
dispersive interactions between the alkane chains, which alter the
ranking of the fast growing crystal directions. The appearance of
preferred orientations for embedded nanocrystals argues that critical
size effects and surface energy considerations favor precritical nuclei
that are oriented with their fast growth axis aligned with the pore
direction. This condition permits the nuclei to achieve critical size
more readily while minimizing the area of planes with high surface
energies, thereby providing a competitive advantage over other
orientations during nucleation. The observation in some cases of two
orientations simultaneously and size-dependent orientations reveals the
delicate balance of free energies among differently oriented nuclei.
Collectively, these observations demonstrate the utility of nanoscale
confinement for investigating the earliest stages of crystal growth.
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title = {Alignment of Organic Crystals under Nanoscale Confinement},
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abstract = {Nanocrystals of alpha,omega-alkanedicarboxylic acids
(HO2C(CH2)(n-2)CO2H, n = 3-13, odd) grown in aligned nanometer-scale
cylindrical pores of nanoporous poly(cyclohexylethylene) monoliths
(p-PCHE) adopt preferred orientations relative to the pore direction.
X-ray diffraction reveals that nanocrystals of malonic acid (n = 3)
grown in 14, 30, and 40 nm diameter pores adopted two preferred mutually
perpendicular orientations simultaneously, each orientation coinciding
with the direction of hydrogen-bonded chains in the solid state.
Nanocrystals of glutaric acid (n = 5) embedded within 30 and 40 nm pores
adopted orientations with hydrogen-bonded chains coincident with the
pore direction, but the chains were perpendicular to the pore direction
in 14 nm pores. Pimelic acid (n = 7) nanocrystals were oriented with
their hydrogen-bonded chains parallel to the pore direction, but
nanocrystals of longer alkane dicarboxylic acids (n = 9, 11, or 13)
adopted orientations in which the their hydrogen-bonded chains
progressively tilted away from the pore direction as the alkane length
was increased. This behavior can be attributed to increasingly strong
dispersive interactions between the alkane chains, which alter the
ranking of the fast growing crystal directions. The appearance of
preferred orientations for embedded nanocrystals argues that critical
size effects and surface energy considerations favor precritical nuclei
that are oriented with their fast growth axis aligned with the pore
direction. This condition permits the nuclei to achieve critical size
more readily while minimizing the area of planes with high surface
energies, thereby providing a competitive advantage over other
orientations during nucleation. The observation in some cases of two
orientations simultaneously and size-dependent orientations reveals the
delicate balance of free energies among differently oriented nuclei.
Collectively, these observations demonstrate the utility of nanoscale
confinement for investigating the earliest stages of crystal growth.},
bibtype = {article},
author = {Ha, Jeong-Myeong and Hamilton, Benjamin D and Hillmyer, Marc A and Ward, Michael D},
journal = {CRYSTAL GROWTH & DESIGN},
number = {9}
}
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Pimelic acid (n = 7) nanocrystals were oriented with\ntheir hydrogen-bonded chains parallel to the pore direction, but\nnanocrystals of longer alkane dicarboxylic acids (n = 9, 11, or 13)\nadopted orientations in which the their hydrogen-bonded chains\nprogressively tilted away from the pore direction as the alkane length\nwas increased. This behavior can be attributed to increasingly strong\ndispersive interactions between the alkane chains, which alter the\nranking of the fast growing crystal directions. The appearance of\npreferred orientations for embedded nanocrystals argues that critical\nsize effects and surface energy considerations favor precritical nuclei\nthat are oriented with their fast growth axis aligned with the pore\ndirection. This condition permits the nuclei to achieve critical size\nmore readily while minimizing the area of planes with high surface\nenergies, thereby providing a competitive advantage over other\norientations during nucleation. The observation in some cases of two\norientations simultaneously and size-dependent orientations reveals the\ndelicate balance of free energies among differently oriented nuclei.\nCollectively, these observations demonstrate the utility of nanoscale\nconfinement for investigating the earliest stages of crystal growth.","bibtype":"article","author":"Ha, Jeong-Myeong and Hamilton, Benjamin D and Hillmyer, Marc A and Ward, Michael D","journal":"CRYSTAL GROWTH & DESIGN","number":"9","bibtex":"@article{\n title = {Alignment of Organic Crystals under Nanoscale Confinement},\n type = {article},\n year = {2012},\n identifiers = {[object Object]},\n pages = {4494-4504},\n volume = {12},\n month = {9},\n publisher = {AMER CHEMICAL SOC},\n city = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA},\n id = {21fff260-a788-3ae3-904b-d8f20466fd60},\n created = {2015-12-14T19:51:23.000Z},\n file_attached = {false},\n profile_id = {3187ec9d-0fcc-3ba2-91e0-3075df9b18c3},\n group_id = {d75e47fd-ff52-3a4b-bf1e-6ebc7e454352},\n last_modified = {2017-03-14T12:30:08.401Z},\n read = {false},\n starred = {false},\n authored = {false},\n confirmed = {true},\n hidden = {false},\n citation_key = {ISI:000308279900028},\n source_type = {article},\n user_context = {Article},\n private_publication = {false},\n abstract = {Nanocrystals of alpha,omega-alkanedicarboxylic acids\n(HO2C(CH2)(n-2)CO2H, n = 3-13, odd) grown in aligned nanometer-scale\ncylindrical pores of nanoporous poly(cyclohexylethylene) monoliths\n(p-PCHE) adopt preferred orientations relative to the pore direction.\nX-ray diffraction reveals that nanocrystals of malonic acid (n = 3)\ngrown in 14, 30, and 40 nm diameter pores adopted two preferred mutually\nperpendicular orientations simultaneously, each orientation coinciding\nwith the direction of hydrogen-bonded chains in the solid state.\nNanocrystals of glutaric acid (n = 5) embedded within 30 and 40 nm pores\nadopted orientations with hydrogen-bonded chains coincident with the\npore direction, but the chains were perpendicular to the pore direction\nin 14 nm pores. Pimelic acid (n = 7) nanocrystals were oriented with\ntheir hydrogen-bonded chains parallel to the pore direction, but\nnanocrystals of longer alkane dicarboxylic acids (n = 9, 11, or 13)\nadopted orientations in which the their hydrogen-bonded chains\nprogressively tilted away from the pore direction as the alkane length\nwas increased. This behavior can be attributed to increasingly strong\ndispersive interactions between the alkane chains, which alter the\nranking of the fast growing crystal directions. The appearance of\npreferred orientations for embedded nanocrystals argues that critical\nsize effects and surface energy considerations favor precritical nuclei\nthat are oriented with their fast growth axis aligned with the pore\ndirection. This condition permits the nuclei to achieve critical size\nmore readily while minimizing the area of planes with high surface\nenergies, thereby providing a competitive advantage over other\norientations during nucleation. 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