Alkane elimination reactions of amino-amino-bis(phenols) H 2 L 1-4 , Salan H 2 L 5 , and methoxy--diimines HL 6,7 with lanthanide tris(alkyl)s, Ln(CH 2 SiMe 3 ) 3 (THF) 2 (Ln ) Y, Lu), respectively, afforded a series of lanthanide alkyl complexes 1-8 with the release of tetramethylsilane. Complexes 1-6 are THFsolvated mono(alkyl)s stabilized by O,N,N,O-tetradentate ligands. Complexes 1-3 and 5 adopt twisted octahedral geometry, whereas 4 contains a tetragonal bipyramidal core. Bearing a monoanionic moiety L 6 (L 7 ), complex 7 (8) is a THF-free bis(alkyl). In complex 7, the O,N,N-tridentate ligand combined with two alkyl species forms a tetrahedral coordination core. Complexes 1, 2, and 3 displayed modest activity but high stereoselectivity for the polymerization of rac-lactide to give heterotactic polylactide with the racemic enchainment of monomer units P r ranging from 0.95 to 0.99, the highest value reached to date. Complex 5 exhibited almost the same level of activity albeit with relatively low selectivity. In contrast, dramatic decreases in activity and stereoselectivity were found for complex 4. The Salan yttrium alkyl complex 6 was active but nonselective. Bis(alkyl) complexes 7 and 8 were more active than 1-3 toward polymerization of rac-LA, however, to afford atactic polylactides due to di-active sites. The ligand framework, especially the "bridge" between the two nitrogen atoms, played a significant role in governing the selectivity of the corresponding complexes via changing the geometry of the metal center. The NMR spectrum of the active species of the rac-lactide oligomer attached to complex 1 demonstrated a coordination-insertion mechanism. In addition it also confirmed that the geometry of the metal center of complex 1 in the solid state was retained in solution (THF) during the polymerization, which contributed significantly to the high selectivity of the complex.

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solventinduced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter χ effZ of the drying films (where χeff is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller χeffZ. As R was decreased from rapid evaporations (∼0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as χ effZ is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.