Stable Heterometallic Cluster Ions based on Werner's Hexol.

Large aqueous ions are interesting because they are useful in materials science (for example to generate thin films) but also because they serve as molecular models for the oxide-aqueous mineral interface where spectroscopy is difficult. Here we show that new clusters of the type M[(µ-OH)2 Co(NH3 )4 ]3 (NO3 )6 (M=Al, Ga) can be synthesized using Werner's century-old cluster as a substitutable framework. We substituted Group 13 metals into the hexol Co[(µ-OH)2 Co(NH3 )4 ]36+ ion to make diamagnetic heterometallic ions. The solid-state structure of the hexol-type derivatives were determined by single-crystal XRD and NMR spectroscopy and confirmed that the solid-state structure persists in solution after dissolution into either D2 O or [D6 ]DMSO. Other compositions besides these diamagnetic ions can undoubtedly be made using a similar approach, which considerably expands the number of stable aqueous heteronuclear ions.

A facile route to old and new cyclophanes via self-assembly and capture.

Cyclophanes are a venerable class of macrocyclic and/or cage compounds that often feature high strain, unusual conformations and quite surprising properties, many of which are legendary in physical organic chemistry. However, the discovery of new, diverse cyclophanes and derivatives has been hindered by syntheses that are traditionally low-yielding, requiring long reaction times, laborious purification steps and often extreme conditions. Herein, we demonstrate a new self-assembly route to a variety of discrete cyclic and caged disulfide structures, which can then be kinetically captured upon sulfur extrusion at room temperature to give a diversity of new thioether (hetera)cyclophanes in high yield. In addition to the synthesis of novel macrocycles (dimers through hexamers), this process provides an improved route to a known macrobicyclic trithiacyclophane. This technique also enables the facile isolation of a tetrahedral macrotricyclic tetrathiacyclophane in two steps at an ambient temperature.

Solution structural characterization of an array of nanoscale aqueous inorganic Ga13-x In x (0 ≤ x ≤ 6) clusters by 1H-NMR and QM computations.

NMR spectroscopy is the go-to technique for determining the solution structures of organic, organometallic, and even macromolecular species. However, structure determination of nanoscale aqueous inorganic clusters by NMR spectroscopy remains an unexplored territory. The few hydroxo-bridged inorganic species well characterized by 1H Nuclear Magnetic Resonance spectroscopy (1H-NMR) do not provide enough information for signal assignment and prediction of new samples. 1H-NMR and quantum mechanical (QM) computations were used to characterize the NMR spectra of the entire array of inorganic flat-Ga13-x In x (0 ≤ x ≤ 6) nanoscale clusters in solution. A brief review of the known signals for µ2-OH and µ3-OH bridges gives expected ranges for certain types of protons, but does not give enough information for exact peak assignment. Integration values and NOESY data were used to assign the peaks of several cluster species with simple 1H-NMR spectra. Computations agree with these hydroxide signal assignments and allow for assignment of the complex spectra arising from the remaining cluster species. This work shows that 1H-NMR spectroscopy provides a variety of information about the solution behavior of inorganic species previously thought to be inaccessible by NMR due to fast ligand and/or proton exchange in wet solvents.

Exploring Anion-Induced Conformational Flexibility and Molecular Switching in a Series of Heteroaryl-Urea Receptors.

Anion binding studies of 1,10-phenanthroline- and 2-pyridyl-substituted urea-based receptors reveal that guest-dependent conformations exist in structural variants related to a previously investigated bipyridyl-based receptor. Dynamic conformational switching persists in a monofunctional pyridyl-urea receptor, and the preorganization provided by a phenanthroline-based analogue promotes convergence of anion coordinating groups to a single guest. Despite this predisposition for anion coordination, the conformational flexibility of the bipyridyl-based receptor provides the most selective motif for H2PO4- coordination. Furthermore, the two new phenanthrolyl- and pyridyl-receptors serve as models of the bipyridyl-based receptor, elucidating accurate stepwise association constants for 1:2 host/guest binding by this receptor, and suggest that oxoanions prefer the embrace of a "U" conformation in 1:1 complexes.

Transmetalation of self-assembled, supramolecular complexes.

Substituting one metal for another in inorganic and organometallic systems is a proven strategy for synthesizing complex molecules, and in some cases, provides the only route to a particular system. The multivalent nature of the coordination in metal-ligand assemblies lends itself more readily to some types of transmetalation. For instance, a binding site can open up for exchange without greatly effecting the many other interactions holding the structure together. In addition to exchanging the metal and altering the local binding environment, transmetalation in supramolecular systems can also lead to substantial changes in the nature of the secondary and tertiary structure of a larger assembly. In this tutorial review we will cover discrete supramolecular assemblies in which metals are exchanged. First we will address fully formed structures where direct substitution replaces one type of metal for another without changing the overall supramolecular assembly. We will then address systems where the disruptive exchange of one metal for another leads to a larger change in the supramolecular assembly. When possible we have tried to highlight systems that use supramolecular self-assembly in tandem with transmetalation to synthesize new structures not accessible through a more direct approach. At the end of this review, we highlight the use of transmetalation in self-assembled aqueous inorganic clusters and discuss the consequences for material science applications.

Chloride-catalyzed, multicomponent self-assembly of arsenic thiolates.

We present the observation that chloride serves as a simple catalyst for the acceleration of a self-assembly reaction between AsCl3 and dithiolate ligands (H2L) to form As2L3 assemblies. Studies on a model monomeric arsenic complex suggest that chloride may accelerate ligand exchange dynamics in pnictogen thiolates in general.

Pnictogen-directed synthesis of discrete disulfide macrocycles.

Cyclic disulfide macrocycles were rapidly synthesized cleanly and selectively from rigid dithiols via oxidation with iodine when activated by pnictogen additives (As and Sb). Macrocycles were confirmed by (1)H-NMR spectroscopy and X-ray crystallography. A p-xylyl-based disulfide trimer and tetramer crystallized in hollow, stacked columns stabilized by intermolecular, sulfur···sulfur close contacts.

Identifying nanoscale M13 clusters in the solid state and aqueous solution: vibrational spectroscopy and theoretical studies.

Raman spectroscopy, infrared spectroscopy, and quantum mechanical computations were used to characterize and assign observed spectral features, highlight structural characteristics, and investigate the bonding environments of [M13(µ3-OH)6(µ2-OH)18(H2O)24](NO3)15 (M = Al or Ga) nanoscale clusters in the solid phase and aqueous solution. Solid-phase Raman spectroscopy was used to reveal that the metal-oxygen (M-O) symmetric stretch (breathing mode) for the Al13 cluster is observed at 478 cm(-1), whereas this same mode is seen at 464 cm(-1) in the Ga13 cluster. The hydroxide bridges in each cluster are weakly Raman active but show slightly stronger infrared activity. The breathing modes associated with the clusters in the solid state are not clearly visible in aqueous solution. This change in behavior in the solution phase may indicate a symmetry breaking of the cluster or exchange events between protons on the ligands and the protic solvent. Overall, each cluster has several unique vibrational modes in the low wavenumber region (<1500 cm(-1)) that are distinct from the parent nitrate salt and other polymeric species with similar structure, which allows for unambiguous identification of the cluster in solution and solid phases.

Elucidating inorganic nanoscale species in solution: complementary and corroborative approaches.

The challenge of defining a length on the nanoscale is non-trivial. For a well-defined inorganic nanoscale species, a size measurement can describe a number of different dimensions (core, shell, solvation sphere). Often size is reported out of context or even inadvertently misrepresented. Since many of the techniques used to measure size depend on significant and sometimes destructive sample preparation, an additional challenge is defining "what size means" for a nanoscale species in solution. In this Concept, the distinction is made between complementary techniques that can be used together to unveil more information about the material in question, and corroborative techniques, which are used to make multiple measurements of the same property. Additionally, corroborative techniques can be used to measure the same property in and out-of solution so as to reveal details about solution behaviour. We highlight various approaches to this characterization challenge in the context of three case studies that demonstrate the use of both complementary and corroborative techniques to elucidate the various functional dimensions of different types of inorganic nanoscale species in solution.

Single nanoscale cluster species revealed by 1H†NMR diffusion-ordered spectroscopy and small-angle X-ray scattering.

A solved structure: The hydrated Ga(13) cluster, [Ga(13)(µ(3)-OH)(6)(µ-OH)(18)(H(2)O)(24)](NO(3))(15)], persists as a discrete nanoscale structure in an aqueous polar solvent at millimolar concentration. SAXS data confirm the presence of Ga(13) in dimethyl sulfoxide (DMSO). In aqueous [D(6)]DMSO (1)H NMR signals for the hydroxo and aquo ligands of Ga(13) were detected, thus showing a cluster with a hydrodynamic radius of (11.2±0.8) Š(see picture).