In the first part of this review, the characteristics of Au-H bonds in gold hydrides are reviewed including the data of recently prepared stable organometallic complexes with gold(I) and gold(III) centers. In the second part, the reports are summarized where authors have tried to provide evidence for hydrogen bonds to gold of the type Au∙∙∙H-X. Such interactions have been proposed for gold atoms in the Au(-I), Au(0), Au(I), and Au(III) oxidation states as hydrogen bonding acceptors and H-X units with X = O, N, C as donors, based on both experimental and quantum chemistry studies. To complement these findings, the literature was screened for examples with similar molecular geometries, for which such bonding has not yet been considered. In the discussion of the results, the recently issued IUPAC definitions of hydrogen bonding and the currently accepted description of agostic interactions have been used as guidelines to rank the Au∙∙∙H-X interactions in this broad range of weak chemical bonding. From the available data it appears that all the intra- and intermolecular Au∙∙∙H-X contacts are associated with very low binding energies and non-specific directionality. To date, the energetics have not been estimated, because there are no thermochemical and very limited IR/Raman and temperature-dependent NMR data that can be used as reliable references. Where conspicuous structural or spectroscopic effects have been observed, explanations other than hydrogen bonding Au∙∙∙H-X can also be advanced in most cases. Although numerous examples of short Au∙∙∙H-X contacts exist in the literature, it seems, at this stage, that these probably make only very minor contributions to the energy of a given system and have only a marginal influence on molecular conformations which so far have most often attracted researchers to this topic. Further, more dedicated investigations will be necessary before well founded conclusions can be drawn.

Unusual storage: An organic nonporous material, p‐tert‐butylcalix[4]arene, sorbs acetylene with high storage density under ambient conditions. It is presumed that gas molecules diffuse through the seemingly nonporous lattice without disrupting the arrangement of the host molecules (see picture; red O, blue C, gray H, yellow void space).

We describe the structure and permeability of a crystalline material that appears to be nonporous in a conventional sense. The material is initially formed as a solvate, and removal of the solvent molecules under relatively mild conditions proceeds via a single-crystal to single-crystal transformation, leaving the host structure intact. Although discrete unoccupied voids of 108 A3 are present in the structure, it is not possible to map open channels that represent an intuitive pathway for guest diffusion. Despite the apparent absence of pores, the material is permeable to a variety of gases including H2, O2, N2, CO, CH4, CO2, and I2. These findings show that porosity in crystalline systems cannot always be rationalized by considering the static structures and that as-yet unknown dynamic and cooperative mechanisms prevail by which porosity can be induced.

Without destruction of monocrystallinity: The conformational switching of a dinuclear metal complex between four distinct states (see picture) occurs without destroying the single crystal. This observation implies a substantial degree of cooperativity between host molecules during guest uptake, release, or exchange.

A discrete rectangular metal-organic complex that stacks to form one-dimensional channels filled with acetonitrile solvent molecules is described. Removal of the solvent under relatively mild conditions proceeds via a single-crystal to single-crystal transformation that leaves the host lattice unaltered. These findings proffer a design strategy for porous materials based on the simple principle that rigid molecular rings cannot pack efficiently and would thus favor the inclusion of guest species whenever possible. Upon guest removal, an efficiently packed new phase can then only be achieved by means of bond cleavage. Thus, achieving crystal porosity by maintaining robust metal-ligand coordination bonds in such discrete cyclic systems directly parallels the strategy employed for MOFs.

An infinite two-dimensional Borromean coordination framework, stabilized by argentophilic interactions, was obtained by the reaction of a flexible ligand with AgBF4.

Frozen but flexible: The conformational flexibility of calixarene molecules is not only limited to solution. It can also manifest itself in single crystals as a response to the right external stimuli.

No abstract