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There are a number of reports on the formation of homochiral lattice on the surface from chiral as well as prochiral molecules. See, for example: (a) Stevens, F.; Dyer, D. J.; Walba, D. M. Angew. Chem., Int. Ed. 1996, 35, 900-901.
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Similar alkyl-chain length dependency was observed in the formation of porous versus nonporous 2D molecular networks of alkoxyformamides: See, ref 34.
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72249100602
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In our attempt to apply a thermodynamic model to evaluate the concentration-dependent polymorph appearance of the bisDBAs; however, we were confronted with difficulties: for example, in the case of 1b, the high sensitivity of the network coverage to the solute concentration (i.e. rapid morphology change within a narrow concentration range) together with the large errors in the surface coverage hamper application of the quantitative treatment (Supporting Information). Furthermore, in the cases of 1c and 1d, the situation is more complicated because of the coexistence of more than two polymorphs.
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72249100835
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The details of the molecular mechanics simulations (MM3) are described in the Supporting Information.
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72249112346
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EpiCalc was downloaded on the Ward's group web site
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EpiCalc was downloaded on the Ward's group web site (http://www.nyu.edu/ fas/dept/chemistry/wardgroup/Software.html).
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112
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72249114921
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A similar observation has been reported: See, ref 19f.
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It has been well-known that chorine exhibits weak Cl-H hydrogen bonding (the distance ranges from 0.26 to 0.29 nm). Thus, we performed MP2/6-31g* optimization of a hexamer of TCB as the simplest case under vacuum. By comparison with six free TCB molecules, the sum of intermolecular interactions was estimated to be -2.48 kcal/mol. This indicates that by weak hydrogen bonding interactions TCB clusters are stabilized.
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118
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note
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Control experiments for bisDBA 1d at the 1-phenyloctane/graphite interface at dilute conditions (1.5 × 10-6 M) or at dry conditions by the evaporation of TCB (1.3 × 10-16 M) resulted in the formation of the porous B and nonporous E structures or nonporous D structure, indicating the role of TCB coadsorption (also Figure S17 of the Supporting Information).
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