Incorporation of a Phosphino(pyridine) Subcomponent Enables the Formation of Cages with Homobimetallic and Heterobimetallic Vertices.

Biological systems employ multimetallic assemblies to achieve a range of functions. Here we demonstrate the preparation of metal-organic cages that contain either homobimetallic or heterobimetallic vertices. These vertices are constructed using 2-formyl-6-diphenylphosphinopyridine, which forms ligands that readily bridge between a pair of metal centers, thus enforcing the formation of bimetallic coordination motifs. Two pseudo-octahedral homometallic MI12L4 cages (MI = CuI or AgI) were prepared, with a head-to-head configuration of their vertices confirmed by X-ray crystallography and multinuclear NMR for AgI. The phosphino-pyridine subcomponent also enabled the formation of a class of octanuclear CdII4CuI4L4 tetrahedral cages, representing an initial example of self-assembled cages containing well-defined heterobimetallic vertices.

Glucose Binding Drives Reconfiguration of a Dynamic Library of Urea-Containing Metal-Organic Assemblies.

A bis-urea-functionalized ditopic subcomponent assembled with 2-formylpyridine and FeII , resulting in a dynamic library of metal-organic assemblies: an irregular FeII4 L6 structure and three FeII2 L3 stereoisomers: left- and right-handed helicates and a meso-structure. This library reconfigured in response to the addition of monosaccharide derivatives, which served as guests for specific library members, and the rate of saccharide mutarotation was also enhanced by the library. The (P) enantiomer of the FeII2 L3 helical structure bound ß-D-glucose selectively over α-D-glucose. As a consequence, the library collapsed into the (P)-FeII2 L3 helicate following glucose addition. The α-D-glucose was likewise transformed into the ß-D-anomer during equilibration and binding. Thus, ß-D-glucose and (P)-3 amplified each other in the product mixture, as metal-organic and saccharide libraries geared together into a single equilibrating system.

Anion Pairs Template a Trigonal Prism with Disilver Vertices.

Here we describe the formation of a trigonal prismatic cage, utilizing 2-formyl-1,8-naphthyridine subcomponents to bind pairs of silver(I) ions in close proximity. This cage is the first example of a new class of subcomponent self-assembled polyhedral structures having bimetallic vertices, as opposed to the single metal centers that typically serve as structural elements within such cages. Our new cage self-assembles around a pair of anionic templates, which are shown by crystallographic and solution-phase data to bind within the central cavity of the structure. Many different anions serve as competent templates and guests. Elongated dianions, such as the strong oxidizing agent peroxysulfate, also serve to template and bind within the cavity of the prism. The principle of using subcomponents that have more than one spatially close, but nonchelating, binding site may thus allow access to other higher-order structures with multimetallic vertices.

Multisite Binding of Drugs and Natural Products in an Entropically Favorable, Heteroleptic Receptor.

The cavities of artificial receptors are defined by how their components fit together. The encapsulation of specific molecules can thus be engineered by considering geometric principles; however, intermolecular interactions and steric fit scale with receptor size, such that the ability to bind multiple guests from a specific class of compounds remains a current challenge. By employing metal-organic self-assembly, we have prepared a triangular prism from two different ligands that is capable of binding more than 20 different natural products, drugs, and steroid derivatives within its prolate cavity. Encapsulation inflates the host, enhancing its ability to bind other guests in peripheral pockets and thus enabling our system to bind combinations of different drug and natural product cargoes in different locations simultaneously. This new mode of entropically favorable self-assembly thus enables central encapsulation to amplify guest-binding events around the periphery of an artificial receptor.

The effect of urban growth on landscape-scale restoration for a fire-dependent songbird.

A landscape-scale perspective on restoration ecology has been advocated, but few studies have informed restoration with landscape metrics or addressed broad-scale threats. Threats such as urban growth may affect restoration effectiveness in a landscape context. Here, we studied longleaf pine savanna in the rapidly urbanizing southeastern United States where a habitat-specialist bird, Bachman's sparrow (Peucaea aestivalis), is closely associated with savanna vegetation structure and frequent fire. Our objectives were to construct a species distribution model for Bachman's sparrow, determine the relationship between fire and urbanization, quantify the urban growth effect (2010-2090), identify potential restoration areas, and determine the interaction between restoration potential and urban growth by 2050. Number of patches, patch size, and isolation metrics were used to evaluate scenarios. The species distribution model was 88% accurate and emphasized multiscale canopy cover characteristics, fire, and percent habitat. Fires were less common <600 m from urban areas, and this fire suppression effect exacerbated urban growth effects. For restoration scenarios, canopy cover reduction by 30% resulted in nearly double the amount of habitat compared to the prescribed fire scenario; canopy cover reduction resulted in larger patch sizes and less patch isolation compared to current conditions. The effect of urban growth on restoration scenarios was unequal. Seventy-four percent of restoration areas from the prescribed fire scenario overlapped with projected urban growth, whereas the canopy cover reduction scenario only overlapped by 9%. We emphasize the benefits of simultaneously considering the effects of urban growth and landscape-scale restoration potential to promote a landscape with greater patch sizes and less isolation.