| This thesis reports the synthesis and single crystal X-ray structures of iron-carboxylate metal-organic frameworks (MOFs), Fe(p-BDC)(DMF)·(H 2O)2 (MOF-220) (a = 19.4697(13), b = 7.2493(5), c = 8.7730(6) A, Pnma ) Fe3(BTC)2(H2O)·(H 2O)11(DMF)4 (MOF-225) (a = 26.7472(9) A, Fm3¯m), Fe(BPDC)(DMF)·(DMF) 0.5 (MOF-106) (a = 7.124(4), b = 15.270(2), c = 12.0109(17) A, beta = 94.604(2)°, C2/ c) and Fe2(m-BDC)2 (DMF) 3·(DMF)(H2O) (MOF-230) (a = 18.341(2), b = 10.0356(11), c = 18.039(2) A, Pca21), composed of square (Fe2(CO2) 4), infinite rod (Fe(CO2)4), and tetrahedral (Fe 2(CO2)4) building units. A second series of related reactions revealed a method for controlling structure periodicity by sulfate-capped vertices, which resulted in formation of isostructural, discrete, metal-organic polyhedra (MOPS) of the general formula, Fe18O9(TDC) 6(SO4)9(OH)3(DMF)15(RO) 3·G (MOPs-100, 101, and 103),(R = ethyl, 1-propyl, or 1-pentyl).; The non-capped version of the Fe3O(RO2)6 (R = carbon or sulfur) trigonal prismatic building unit was linked by ditopic benzene links to produce two 3-periodic frameworks, [Fe3O( p-BDC)3(DMF)3][FeCl4]·(DMF) 3 (MOF-235) (a = 12.531(3), c = 18.476(11) A, P6¯2c) and [Fe3O( m-BDC)3(pyr)3]·(pyr)0.5(H 2O)1.5 (MOF-236) (a = 13.017(4), c = 14.896(8) A, P6¯2c), having a new topology termed acs. Three sites of the trigonal prismatic unit can alternately be capped with sulfate to yield the triangular unit, Fe3O(SO4)3(CO2)3. This was joined by either ditopic (phenyl, biphenyl, terphenyl, or hydropyrene) or tritopic (benzenetriphenyl) links to give the isostructural truncated tetrahedra and truncated heterocubane of general formula, [NH2(CH3) 2]8[Fe12O4(SO4)12(link) x(py)12]·G (x = 6 for linear or 4 for trigonal), respectively (a = 32.6504(13) A, F4¯3m for IRMOP-50) (a = 25.8626(9), b = 26.8359(9), c = 28.1926(10) A, alpha = 75.1380(10)°, beta = 88.5680(10)°, gamma = 63.7830(10)°, P1¯ for triclinic IRMOP-51) (a = 38.508(9) A, F4¯3m for cubic IRMOP-51) (a = 43.730(4), b = 22.671(2), c = 41.328(4) A, beta = 120.182(2)°, C2/ c for IRMOP-52) (a = 31.642(3), b = 31.762(3), c = 31.830(3) A, alpha = 75.847(2)°, beta = 75.264(2)°, gamma = 60.155(2)°, P1¯ for IRMOP-53) (a = 26.8549(13), c = 40.9221(19) A, I41/a for MOP-54).; These MOPs can be linked further by bifunctional 1,2-bis-4-pyridylethane to give a three-periodic MOF [NH2(CH3)2] 8[Fe12O4(SO4)12(BPDC) 6(bpe)6]·G (MOF-500) (a = 38.641(6) A, F4¯3m).; Truncated tetrahedral and truncated heterocubiodal MOPs show porosity and uptake of N2, CO2, Ar, H2, CH4, and benzene. The isotherms exhibit Type I behavior, indicative of permanent microporosity with apparent surface areas ranging from 387 to 480 m 2/g. |
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