A Molecular Strategy to Lock-in the Conformation of a Perylene Bisimide-Derived Supramolecular Polymer.

Locking-in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)-derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure-function relationships. Experiments that exploit variable-temperature ground-state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non-covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid-state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non-covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100-mV stabilization of the conduction band energy when compared to that recorded for the non-covalent assembly.

Reconfiguration of π-conjugated superstructures enabled by redox-assisted assembly.

We show that n-doping supramolecular assemblies built from perylene diimide units provides a means to modulate the structure-function properties of these materials. In addition to highlighting the design principles, a combination of spectroscopic and microscopic characterization correlates an increase in the free-exciton bandwidth with the formation of mesoscale hierarchical superstructures.

The Consequences of Teenage Childbearing: Consistent Estimates When Abortion Makes Miscarriage Nonrandom.

Miscarriage, even if biologically random, is not socially random. Willingness to abort reduces miscarriage risk. Because abortions are favorably selected among pregnant teens, those miscarrying are less favorably selected than those giving birth or aborting but more favorably selected than those giving birth. Therefore, using miscarriage as an instrument is biased towards a benign view of teen motherhood while OLS on just those giving birth or miscarrying has the opposite bias. We derive a consistent estimator that reduces to a weighted average of OLS and IV when outcomes are independent of abortion timing. Estimated effects are generally adverse but modest.