Directed assembly of structures using coordination and covalent bonding.

In this work we present the synthesis and structural characterization of three new metal organic frameworks (MOFs): MOF-103, Zn([C2H 4]C6H2[CO2]2)(H2O)• (C3H7N)0.9(H2O)1.5, IRMOF-6, Zn4O([[C2H4]C6H 2[CO2]2)3•(C5H 11N)5.5, and MOF-49, Zn7(C6H2 [CO2]2)6(OH)4(H2O) 2•(C3H7N)6(H2O) 4. The crystal structures of MOF-103 and IRMOF-6 revealed analogous structures to previously studied MOF-2 and MOF-5, respectively. Reversible Type I isotherms were measured on the evacuated frameworks of MOF-103 and IRMOF-6 for many different gases and organic vapors and pore volumes and Langmuir surface areas were calculated at Vp = 0.11cm3/g and Slangmuir = 330 m2/g and V p = 0.60 cm3/cm3 and S langmuir = 2630 m2/g respectively. Methane uptake was measured for IRMOF-6 and found to be 155 cm3 (STP)/cm 3 at 298K and 36 atm. The crystal structure of MOF-49 is constructed from large cuboctahedral Zn-O-C cluster vertices linked by isophthalate into a 3-D framework. Additionally, this thesis reports the general synthesis and structural characterization of tris-(p-cyanophenyl)-s-triazine[Pmn2(1), a = 22.316(6) A, b = 10.578(3) A, c = 4.0770(11) A, V = 962.4(4) A3], tris-(m-cyanophenyl)- s-triazine [P(-1), a = 7.2840(7) A, b = 9.2599(9) A, c = 13.8470(13) A, alpha = 79.886(2)°, beta = 87.956(2)°, gamma = 82.926(2)°, V = 912.36(15) A3], and a pentameric compound [P(-1), a = 3.786(5) A, b = 18.358(5) A, c = 22.560(5) A, alpha = 105.413(5)°, beta = 93.431(5)°, gamma = 91.740(5)°, V = 1507(2) A3] (based on isophthalonitrile). Tris-( p-cyanophenyl)-s-triazine and tris-(m-cyanophenyl)- s-triazine were reacted to form polymeric materials that were subsequently characterized by EA, FT-IR, EPR, SQUID, SEM and TEM. Using TEM, a minority crystalline phase was observed and an electron diffraction pattern obtained. Tris-(2,6-dichloro-s-triazine)-amine was synthesized from the metathesis of cyanuric chloride and lithium nitride and characterized [R-3, a = b = 19.278(2) A, , c = 7.4379(11) A, V = 2393.9(5) A 3]. The structure was determined and found it to be a structural and compositional model for the previously proposed graphitic forms of C 3N4. The three dimensional structure of the compound suggests new three dimensional topologies for C3N4 (SrSi 2 or ThSi2). The validity of these new forms was assessed by DFT calculations on models of the extended solids.Ph.D.Inorganic chemistryPolymer chemistryPure SciencesUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/123524/2/3082634.pd