Tri-metal Secondary Building Units: Toward the Design of Thermally Robust Crystalline Coordination Polymers

Three new crystalline coordination polymers [Mn3(TDC)4(H2O)4](2,6-lutidine)2(H2O)3 1, P-1, a = 11.351(3), b = 11.391(3), c = 11.480(3), α = 112.838(4), β = 90.696(4), γ = 99.328(4); [Zn3(1,4-BDC)3(EtOH)2] 2, C2/c, a = 19.1308(9), b = 10.6088(5), c = 16.2221(7), β = 108.79(1); and [Zn3(1,3-BDC)3(py)2](MeOH) 3, P2(1)/c, a = 17.142(3), b = 21.544(4), c = 11.805(2), β = 106.441(3); TDC = 2,5-thiophenedicarboxylate, BDC = benzedicarboxylate, have been synthesized by linking tri-metal nodes with poly-carboxylate ligands. Single crystal x-ray analysis shows that 1 is composed of (4,4) 2-D grids with A–A stacking while 2 is comprised of (6,3) triangular networks in an A–B–C stacking pattern and 3 has formed a distorted cubic diamondoid topology. Tri-metal nodes are located at the vertexes of each network. Thermal gravimetric analysis demonstrates that 1 and 2 are thermally robust structures with network decomposition temperatures of 375 °C and 460 °C respectively. Tri-metal Secondary Building Units: Toward the Design of Thermally Robust Crystalline Coordination Polymers Brian S. Luisi, Zhenbo Ma and Brian Moulton* Tri-metal nodes are shown to be an advantageous target in the synthesis of 2-D crystalline coordination polymers with high thermal stability.