The reaction system composed of triethanolamine (TEA) and tetrathiovanadate in the presence of MeONa (MeOLi) or NaNH2 was studied to afford vanadium and alkali metal TEA complexes. Complexes {M subset ofV(6)O(6)[N(CH2CH2O)(2)(CH2CH2OH)](6)}(2)S-6 (M = Na (1), Li (2)) contain two cyclic V-(IV) [12]metallacrown-6 cations linked by a polysulfide S-6(2-) anion. Also separated from the reaction system is a novel sodium TEA complex {[Na(TEA)](2)S-6}(n), (3), in which parallel coordination chains [Na(TEA)(+)](n) are connected by O-H . . .S hydrogen bonds forming 3-D network structure. Variable-temperature conductance of 3 was determined to display semiconductor feature. The desulfurization of VS43- was observed to form S-6(2-) anion and,or S-8 molecule in the synthetic reactions of 1-3. A striking contrast was noted that MoS42- did not desulfurize in the similar reaction to that of VS43- With TEA, and a Na/TEA complex containing MoS42-, (Et4N)(2)[Na-2(mu -TEA)(2)(CH3OH)(2)](MoS4)(2) (4), was Obtained instead. The S . . .H-O and O . . .H-O hydrogen bonds play an important role in forming the one- or three-dimensional structures for all these complexes by the linkages between clusters and chains. The IR spectrum indicates the structural similarity of complexes 1 and 2. For complex 4, the Mo=S stretch vibration at 468 cm(-1) showing widening and slight red-shift and the slight movement of the H-1 NMR signals of TEA ligand to downfield are considered to be the influence of the S . . .H-O hydrogen bonds. Variable temperature magnetic susceptibility data were collected for complex 1. The effect magnetic moment per V-6 unit varies gradually from 4.04 mu (B) at 300 K to 6.24 mu (B) at 5 K, exhibiting ferromagnetic interaction. Heisenberg-type vector-coupling model and molecular field approximation were used to treat the interaction between the paramagnetic sites and gave a good fitting result: J = 3.97 cm(-1), J ' = 1.99 cm(-1), g = 1.99, F = 3.64 x 10(-3). Density functional calculation was also performed to complex 1 and its Li, K analogues. The lowest total bonding energy of -874.001 eV was obtained for [Na subset ofV(6)(mu (3)-O)(6)] complex containing six unpaired electrons, indicating the stability of a V-6 system with six independent spins S = 1/2. When the alkali metal ion is inserted into the [V-6(mu (3)-O)6] cavity, the positive values of the bonding interaction (E-b) indicate that the insertion depresses the total energy and that complexes 1 and 2 together with K+ complex may exist. However, the lowest E-b value of the K+ complex implies its instability.