Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

First excitations of the spin 1/2 Heisenberg antiferromagnet on the kagomé lattice

We study the exact low energy spectra of the spin 1/2 Heisenberg antiferromagnet on small samples of the kagomé lattice of up to N=36 sites. In agreement with the conclusions of previous authors, we find that these low energy spectra contradict the hypothesis of Néel type long range order. Certainly, the ground state of this system is a spin liquid, but its properties are rather unusual. The magnetic () excitations are separated from the ground state by a gap. However, this gap is filled with nonmagnetic () excitations. In the thermodynamic limit the spectrum of these nonmagnetic excitations will presumably develop into a gapless continuum adjacent to the ground state. Surprisingly, the eigenstates of samples with an odd number of sites, i.e. samples with an unsaturated spin, exhibit symmetries which could support long range chiral order. We do not know if these states will be true thermodynamic states or only metastable ones. In any case, the low energy properties of the spin 1/2 Heisenberg antiferromagnet on the kagomé lattice clearly distinguish this system from either a short range RVB spin liquid or a standard chiral spin liquid. Presumably they are facets of a generically new state of frustrated two-dimensional quantum antiferromagnets. Received: 27 November 1997 / Accepted: 29 January 1998     

On the exceptional series,and its descendantsLa série exceptionnelle,et sa descendance

Many of the striking similarities which occur for the adjoint representation of groups in the exceptional series (cf. [1–3]) also occur for certain representations of specific reductive subgroups. The tensor algebras on these representations are easier to describe (cf. [4,5,7]), and may offer clues to the original situation.The subgroups which occur form a Magic Triangle, which extends Freudenthal's Magic Square of Lie algebras. We describe these groups from the perspective of dual pairs, and their representations from the action of the dual pair on an exceptional Lie algebra. To cite this article: P. Deligne, B.H. Gross, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 877–881.     

Flatness in analytic mappings I. On an announcement of Hironaka

We present a stratification by “normal flatness” associated to an analytic mapping, analogous to Hironaka's classical result for analytic spaces. Our construction is based on a generic normal flatness theorem for mappings, proved using techniques concerning the variation of modules of meromorphically parametrized formal power series [1]. The existence of such a stratification was announced by Hironaka [13], but the other claims made in [13] are false. Counterexamples are also presented here.     

Carnot-Carathéodory Metric and Gauge Fluctuation in Noncommutative Geometry

Gauge fields have a natural metric interpretation in terms of horizontal distance. The latest, also called Carnot-Carathéodory or subriemannian distance, is by definition the length of the shortest horizontal path between points, that is to say the shortest path whose tangent vector is everywhere horizontal with respect to the gauge connection. In noncommutative geometry all the metric information is encoded within the Dirac operator D. In the classical case, i.e. commutative, Connes’s distance formula allows to extract from D the geodesic distance on a riemannian spin manifold. In the case of a gauge theory with a gauge field A, the geometry of the associated U(n)-vector bundle is described by the covariant Dirac operator D+A. What is the distance encoded within this operator? It was expected that the noncommutative geometry distance d defined by a covariant Dirac operator was intimately linked to the Carnot-Carathéodory distance dh defined by A. In this paper we make precise this link, showing that the equality of d and d _H strongly depends on the holonomy of the connection. Quite interestingly we exhibit an elementary example, based on a 2 torus, in which the noncommutative distance has a very simple expression and simultaneously avoids the main drawbacks of the riemannian metric (no discontinuity of the derivative of the distance function at the cut-locus) and of the subriemannian one (memory of the structure of the fiber).