Steven R. Breeze

Synthesis and characterization of SrCu2(O2CR)3(bdmap)3 and Bi2(O2CCH3)4(bdmap)2(H2O) (R = CH3, CF3; bdmap = 1,3-bis(dimethylamino)-2-propanolato)

Abstract New mixed metal complexes SrCu 2 (O 2 CR) 3 (bdmap) 3 (R = CF 3 ( 1a ), CH 3 ( 1b )) and a new dinuclear bismuth complex Bi 2 (O 2 CCH 3 ) 4 (bdmap) 2 (H 2 O) ( 2 ) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF 2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi 2 O 3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2 J = 34.0(8) cm −1 . Crystal data for 1a : C 27 H 51 N 6 O 9 F 9 Cu 2 Sr/THF, monoclinic space group P2 1 /m, a = 10.708(6), b = 15.20(1), c = 15.404(7) A , β = 107.94(4)°, V = 2386(2) A 3 , Z = 2 ; for 1b : C 27 H 60 N 6 O 9 Cu 2 Sr/THF, orthorhombic space group Pbcn, a = 19.164(9), b = 26.829(8), c = 17.240(9) A , V = 8864(5) A 3 , Z = 8 ; for 2 : C 22 H 48 O 11 N 4 Bi 2 , monoclinic space group P2 1 /c, a = 17.614(9), b = 10.741(3), c = 18.910(7) A , β = 109.99(3)°, V = 3362(2) A 3 , Z = 4 .

Structural interconversion facilitated by a bifunctional ligand: acovalently linked 2D CuII sheet[Cu(3-pyOH)2(O2CCF3)2]n and a hydrogen-bond linked 2D CuII sheet[Cu(3-pyOH2)(O2CCF3)2(thf)2]n

A covalently linked 2D Cu II compound, [Cu(O 2 CCF 3 ) 2 (3-pyOH) 2 ] n 1 (3-pyOH = 3-hydroxypyridine), when dissolved in thf, undergoes conversion to a hydrogen-bond linked 2D Cu II compound, [Cu(O 2 CCF 3 ) 2 (3-pyOH) 2 (thf) 2 ] 2, which upon heating or standing at 23 °C for a few hours is converted back to compound 1 by losing the coordinated thf molecule; weak ferromagnetic interactions between Cu II centres dominate in both compounds.