Covalent Titanium(IV)–Aryloxide Network Materials: 4,4′-Biphenoxide 3D and Polyphenolic 2D Motifs

Abstract

The three- and two-dimensional covalent metal–organic network (CMON) compounds {[Ti(μ1,6:η2,η1-4,4′-OC12H8O)0.5(μ1,6:η2,η1-4,4′-OC12H8O)(OiPr)(HOiPr)]2·THF}n (1) and {[Ti(μ1,3-1,3-OC6H4O)(μ-1,3-OC6H4OH)(1,3-OC6H4OH) (HOiPr)]2}n (2) were synthesized by treatment of Ti(OiPr)4 with 4,4′-dihydroxybiphenyl in THF and resorcinol in CS2, respectively, at 100°C. Diffraction data was collected at the Cornell High Energy Synchrotron Source (CHESS) because of the small, weakly diffracting nature of the crystals. 1 (C26H31O5.5Ti, monoclinic, P21, a=10.137(2), b=15.988(3), c=15.745(3), β=107.76(3)°, Z=4, R=0.0858) and 2 (C21H22O7Ti, monoclinic, P21/c, a=11.955(2), b=16.275(3), c=11.028(2), β=113.25(3)°, Z=4, R=0.0550) are both based upon similar edge-sharing bioctahedral dititanium building blocks, (i.e., Ti2(μ-OAr)2). Six connections per dititanium unit constrain the structural motif of 1 to be base-centered. Four μ1,3-diphenoxides per dititanium core in 2 connect to provide a rectangular net, but the regiochemistry of resorcinol ultimately restricts its dimensionality. The structures suggest design elements based on the number and geometry of connecting organic linkages.