Zhi-Hui Liu

Rationally designed and controlled syntheses of different series of 4d–4f heterometallic coordination frameworks based on lanthanide carboxylate and Ag(IN)2 substructures

Different series of Ln(III)–Ag(I) heterometallic coordination frameworks, namely LnAg(OAc)(IN)2(H2O)·(ClO4) [Ln = Tb (1a); Ho (1b), HOAc = acetic acid, HIN = isonicotinic acid], LnAg2(OX)0.5(IN)3(H2O)1.5·(ClO4) [Ln = Nd (2a); Eu (2b) Tb (2c), OX = oxalate], Eu2Ag3(OX)0.5(IN)6(NO3)(ClO4)(H2O)3·2(H2O) (3), LnAg(OX) (IN)2(H2O) [Ln = Ce (4a); Sm (4b)], LnAg(Mal)(IN)2(H2O) [Ln = La (5a); Nd (5b), H2Mal = malonic acid], Ln3Ag4(Lac)2(IN)8(H2O)5·2(ClO4)·2.5(H2O) [Ln = La (6a); Lu (6b), HLac = lactic acid], Sm3Ag4(Lac)2(IN)8(H2O)4·2(ClO4)·2.5(H2O) (7), and Eu2Ag3(S-Lac)(IN)6(H2O)4·2(ClO4)·4(H2O) (8) were successfully synthesized by systematic variation of reaction parameters such as initial reactants, reaction time, pH, temperature, etc. Compounds 1a and 1b represent 3D coordination frameworks that are constructed from adjacent lanthanide carboxylate layers and pillared Ag(IN)2 units. Compounds 2a, 2b and 2c comprise of 2D Ln-carboxylate-Ag layered networks and pillared Ag(IN)2 units. Compound 3 exhibits 3D coordination frameworks that are built up from the assembly of europium-carboxylate layers and pillared Ag(IN)2 units. 3D coordination networks of compounds 4a and 4b containing tetranuclear Ln2Ag2 cores are constructed from 2D cerium oxalate layers and tilted pillared Ag(IN)2 subunits. Compounds 5a and 5b display attractive 3D coordination frameworks constructed of 2D lanthanum malonate chains and pillared Ag(IN)2 units. Compounds 6a and 6b are 2D coordination frameworks comprised of 1D racemic lanthanum carboxylate chains and pillared Ag(IN)2 units. The crystal structure of 7 is almost the same as that of 6a and 6b, only one less coordination water molecule is coordinated to its metal centre. Compound 8, which spontaneously resolved upon crystallization, represents the first example of a 3D Ln–Ag coordination framework built up from 1D europium-carboxylate chains containing chiral molecules and pillared Ag(IN)2 units.

A series of 3d–4f heterometallic coordination polymers constructed from size-tunable copper halide clusters and lanthanide-organic motifs

A series of three-dimensional (3D) lanthanide–copper coordination polymers, namely [Ln2(NA)6Cu6Br6(H2O)4]·3.5H2O] [Ln = Sm (1), Eu (2), Tb (3), NA− = nicotinate], [Ln(NA)2Cu2Br2(C2O4)0.5(H2O)2]·2H2O [Ln = Gd (4), Er (5), C2O4 = oxalate], [Ln(NA)2Cu3Br3(OAc)(H2O)] [Ln = Sm (6), Eu (7), Tb (8), OAc = acetate], [Er2(NA)6Cu7Br7(H2O)4]·2H2O (9) and [Gd(NA)3Cu3Cl3(H2O)2]·H2O (10) have been hydrothermally synthesized and structurally characterized. Compounds 1–3 are constructed from Ln–organic chains and two distinct Cu4Br4 clusters possessing a (411.64)2(414.67)2(418.610)(49.6)2 topology. Compounds 4 and 5 are composed of two-dimensional (2D) Ln–organic layers and cubane-like Cu4Br4 clusters possessing a (43.66.8)(43)(46.66.83) topology. Compounds 6–8 can be viewed as the connection between Ln–organic chains and prism-like Cu6Br6 clusters with 4,6T50 topology. Compound 9 is constructed by Er–organic chains and dicubane-like Cu8Br7 clusters possessing a fluorite (flu) topology. Compound 10 consists of Gd–organic chains and inorganic Cu3Cl3 chains with tcj/hc topology. The diversity of the products demonstrates that the auxiliary ligand, pH value, reaction temperature and anion have significant effect on the construction of the structures. Moreover, the photoluminescence of 1–3 and 6–8, and the magnetism of 9 and 10 were investigated.