pH-Dependent Assembly of Molecular Capsule,2D and 3D Coordination Polymers

Three lanthanum/4-sulfocalix[4]arene complexes,namely,H2[(H4CAS)La(H2O)7]2· H2[(H4CAS)La(H2O)7]2·2C2H5OH·12H2O(1),[H(H4CAS)La(H2O)5]·5H2O(2)and [(H4CAS)La-(H2O)4(NO3)La(H2O)5]·7H2O(3),have been synthesized at different pH conditions.Complex 1,which exhibits the structure of "molecular capsule" containing the guest of C2H5OH molecule,is formed at pH = 1.At pH = 2～3,a two-dimensional(2D)coordination polymer of 2 is formed.Further increase of the pH value to 5 leads to the three-dimensional(3D)coordination polymer of 3.Crystal data for 1:monoclinic,space group P21/n,a = 10.8743(16),b = 25.957(4),c = 15.863(2),β = 94.763(2)°,V = 4462.1(11)3,Mr = 1160.87,Z = 4,F(000)= 2376,R = 0.0370 and wR = 0.0936;Crystal data for 2:tetragonal,space group P4/n,a = 11.6593(16),c = 14.069(4),V = 1912.5(6)3,Mr = 1114.81,Z = 2,F(000)= 1136,R = 0.0849 and wR = 0.1906;and those for 3:triclinic,space group P1,a = 10.4588(16),b = 14.995(2),c = 16.699(3),α = 65.446(3),β = 83.487(3),γ = 73.305(3)°,V = 2281.6(6)3,Mr = 1367.76,Z = 2,F(000)= 1368,R = 0.0423 and wR = 0.1183.