Fascination with supramolecular chemistry over the last few decades has led to the synthesis of an ever-increasing number of elegant and intricate functional structures with sizes that approach nanoscopic dimensions Today, it has grown into a mature field of modern science whose interfaces with many disciplines have provided invaluable opportunities for crossing boundaries both inside and between the fields of chemistry, physics, and biology This chemistry is of continuing interest for synthetic chemists; partly because of the fascinating physical and chemical properties and the complex and varied aesthetically pleasing structures that supramolecules possess For scientists seeking to design novel molecular materials exhibiting unusual sensing, magnetic, optical, and catalytic properties, and for researchers investigating the structure and function of biomolecules, supramolecular chemistry provides limitless possibilities Thus, it transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field

In the early 1960s, the discovery of ‘crown ethers’, ‘cryptands’ and ‘spherands’ by Pedersen,1 Lehn,2 and Cram3 respectively, led to the realization that small, complementary molecules can be made to recognize each other through non-covalent interactions such as hydrogen-bonding, charge-charge, donor-acceptor, π-π, van der Waals, etc Such ‘programmed’ molecules can thus be self-assembled by utilizing these interactions in a definite algorithm to form large supramolecules that have different physicochemical properties than those of the precursor building blocks Typical systems are designed such that the self-assembly process is kinetically reversible; the individual building blocks gradually funnel towards an ensemble that represents the thermodynamic minimum of the system via numerous association and dissociation steps By tuning various reaction parameters, the reaction equilibrium can be shifted towards the desired product As such, self-assembly has a distinct advantage over traditional, stepwise synthetic approaches when accessing large molecules

It is well known that nature has the ability to assemble relatively simple molecular precursors into extremely complex biomolecules, which are vital for life processes Nature’s building blocks possess specific functionalities in configurations that allow them to interact with one another in a deliberate manner Protein folding, nucleic acid assembly and tertiary structure, phospholipid membranes, ribosomes, microtubules, etc are but a selective, representative example of self-assembly in nature that is of critical importance for living organisms Nature makes use of a variety of weak, non-covalent interactions such as hydrogen–bonding, charge–charge, donor–acceptor, π-π, van der Waals, hydrophilic and hydrophobic, etc interactions to achieve these highly complex and often symmetrical architectures In fact, the existence of life is heavily dependent on these phenomena The aforementioned structures provide inspiration for chemists seeking to exploit the ‘weak interactions’ described above to make scaffolds rivaling the complexity of natural systems

The breadth of supramolecular chemistry has progressively increased with the synthesis of numerous unique supramolecules each year Based on the interactions used in the assembly process, supramolecular chemistry can be broadly classified in to three main branches: i) those that utilize H-bonding motifs in the supramolecular architectures, ii) processes that primarily use other non-covalent interactions such as ion-ion, ion-dipole, π–π stacking, cation-π, van der Waals and hydrophobic interactions, and iii) those that employ strong and directional metal-ligand bonds for the assembly process However, as the scale and degree of complexity of desired molecules increases, the assembly of small molecular units into large, discrete supramolecules becomes an increasingly daunting task This has been due in large part to the inability to completely control the directionality of the weak forces employed in the first two classifications above Coordination-driven self-assembly, which defines the third approach, affords a greater control over the rational design of 2D and 3D architectures by capitalizing on the predictable nature of the metal-ligand coordination sphere and ligand lability to encode directionality Thus, this third strategy represents an alternative route to better execute the “bottom-up” synthetic strategy for designing molecules of desired dimensions, ranging from a few cubic angstroms to over a cubic nanometer For instance, a wide array of 2D systems: rhomboids, squares, rectangles, triangles, etc, and 3D systems: trigonal pyramids, trigonal prisms, cubes, cuboctahedra, double squares, adamantanoids, dodecahedra and a variety of other cages have been reported As in nature, inherent preferences for particular geometries and binding motifs are ‘encoded’ in certain molecules depending on the metals and functional groups present; these moieties help to control the way in which the building blocks assemble into well-defined, discrete supramolecules4

Since the early pioneering work by Lehn5 and Sauvage6 on the feasibility and usefulness of coordination-driven self-assembly in the formation of infinite helicates, grids, ladders, racks, knots, rings, catenanes, rotaxanes and related species,7 several groups - Stang,8 Raymond,9 Fujita,10 Mirkin,11 Cotton12 and others13,14 have independently developed and exploited novel coordination-based paradigms for the self-assembly of discrete metallacycles and metallacages with well-defined shapes and sizes In the last decade, the concepts and perspectives of coordination-driven self-assembly have been delineated and summarized in several insightful reviews covering various aspects of coordinationdriven self-assembly15 In the last decade, the use of this synthetic strategy has led to metallacages dubbed as “molecular flasks” by Fujita,16 and Raymond and Bergman,17 which due to their ability to encapsulate guest molecules, allowed for the observation of unique chemical phenomena and unusual reactions which cannot be achieved in the conventional gas, liquid or solid phases Furthermore, these assemblies found applications in supramolecular catalysis18,19 and as nanomaterials as developed by Hupp20 and others21,22

This review focuses on the journey of early coordination-driven self-assembly paradigms to more complex and discrete 2D and 3D supramolecular ensembles over the last decade We begin with a discussion of various approaches that have been developed by different groups to assemble finite supramolecular architectures The subsequent sections contain detailed discussions on the synthesis of discrete 2D and 3D systems, their functionalizations and applications

Supramolecular coordination: self-assembly of finite two- and three-dimensional ensembles.

2.1.2. Low Topology/Framework Density 1003 2.1.3. Side Group Directed Superstructures 1003 2.2. Synthesis Considerations 1003 2.3. Special Properties 1004 3. Metal Imidazolate Frameworks 1004 3.1. Chains and Rings 1004 3.2. Zeolitic and Zeolite-like Frameworks 1006 3.2.1. SOD-Type Zinc(II) 2-Methylimidazolate 1007 3.3. Nonporous 4-Connected Networks 1010 3.4. Polyimidazolates 1011 4. Metal Pyrazolate Frameworks 1011 4.1. Clusters and Chains 1011 4.2. 3D Networks Based on Polypyrazolates 1012 5. Metal 1,2,4-Triazolate Frameworks 1014 5.1. Simple 3-Connected Networks 1015 5.2. Quasi-Imidazolates 1018 5.3. With Coordinative Substituents 1019 5.4. With Secondary Counterions and/or Ligands 1021 6. Metal 1,2,3-Triazolate Frameworks 1023 7. Metal Tetrazolate Frameworks 1025 7.1. Univalent Coinage-Metal Tetrazolate Frameworks 1025

Metal Azolate Frameworks: From Crystal Engineering to Functional Materials

Carbon-hydrogen bonds, especially those of saturated (s$) carbon centres, are normally regarded as being chemically inert. Generally, the C-H group is not thought of as a potential ligand which can have a structural role or play an energetically significant part in ground states or in reaction intermediates. In this article we review recent observations which show that there are in fact many circumstances in which a carbon-hydrogen group will interact with a transition metal centre with formation of a two-electron three-centre bond and that the extent of the interaction is such as to have a marked effect on the molecular and electronic structure and hence reactivity of the molecule. We propose the term “agostic” which will be used to discuss the various manifestations of covalent interactions between carbon-hydrogen groups and transition metal centres in organometallic compounds l . The word agostic will be used to refer specifically to situations in which a hydrogen atom is covalently bonded simultaneously to both a carbon atom and to a transition metal atom. The agostic C-H-M bond is similar to the familiar and long known bridging hydrogen systems which occur in B-H-B, M-H-M, and B-H-M groups. The C-H-M bonds are a recent observation but as will be discussed below, they are probably very much more common than hitherto suspected. Since carbon-hydrogen bonds are a ubiquitous feature of organometallic compounds we have found it useful to define

Carbon-Hydrogen-Transition Metal Bonds

Recently accumulated experimental evidence for aurophilic interactions in and between molecular gold(I) compounds and the results of pertinent theoretical calculations are reviewed for the period from 2007 to mid-2011. The influence of the intra- and intermolecular bonding contacts between the closed-shell metal centres, Au–Au, on the molecular and crystal structures, and the consequences of these effects for the chemical and physical properties of gold compounds are summarized for the various classes of mono- and polynuclear systems. The literature survey builds on the contents of previous reviews and relates new experimental and theoretical findings to earlier observations (353 references).

Aurophilic interactions as a subject of current research: an up-date

Kraitchman has shown that a single isotopic substitution on an atom is sufficient to determine directly the coordinates of that atom with respect to the principal axes of the original molecule. Kraitchman's formulas represent exact solutions of the equations for the equilibrium moments of inertia. However, the effects of the zero‐point vibrations are such that the coordinates obtained by substitution from the ground state moments of inertia I0 are systematically less than r0. These coordinates have here been called r (substitution) or rs, and it is found that rs≃(r0+re)/2, and Is= ∑ imirsi2≃(I0+Ie)/2.In the usual method of solution, the coordinate of one atom is determined from the equation for I0, and therefore the difference I0—Is must be made up by this one coordinate. This introduces a large error in the structures normally determined from ground state constants, and results in variations of 0.01 A in structures determined from different sets of isotopic species. If instead, we obtain the structure on...

A new criterion for the determination of molecular structures from ground state rotational constants

The mixed-valence Au I /Au III complex [Au(CH 2 ) 2 PPh 2 ] 2 Br 2 has been prepared by two methods: reduction of [Au(CH 2 ) 2 PPh 2 ] 2 Br 4 with AgCN; oxidation of [Au(CH 2 ) 2 PPh 2 ] 2 (CN) 2 by Br 2 , followed by spontaneous reduction. The CH 2 Cl 2 solvate of the mixed-valence complex was characterized crystallographically: orthorhombic, Pcmn. The X-ray photoelectron spectroscopy study of this complex confirmed the crystallographic results

Synthesis of a mixed-valence gold(I)/gold(III) complex, [Au(CH2)2PPh2]2Br2, and its characterization by x-ray crystallography and x-ray photoelectron spectroscopy

Structural characterization of a linear [Au.cntdot..cntdot..cntdot.Pt.cntdot..cntdot..cntdot.Au] complex, Au2Pt(CH2P(S)Ph2)4, and its oxidized linear metal-metal bonded [Au-Pt-Au] product, Au2Pt(CH2P(S)Ph2)4Cl2

Sulfur-containing gold(III) chelates and their use in heterovalent dimer synthesis: crystal structures of AuIII[CH2P(S)Ph2]2Br, [AuIII[S2P(OH)Ph]2]Cl, and AuIII[CH2P(S)Ph2][S2CN(Et)2]2

The reaction of ClAuPPh3 with sodium 3,5-diphenylpyrazolate in tetrahydrofuran with added AgOCOPh yields hexakis(µ-3,5-diphenylpyrazolato-N,N′)-hexagold(I)(1), a compound with a novel 18-membered twisted ring and a fused-edge bi-tetrahedral grouping of gold atoms, as determined crystallographically.

The synthesis and crystal structure of a novel gold(I)–pyrazolate hexamer containing an 18-membered inorganic ring

[Au(CH2)2PPH2]2, (1), reacts with neat CH2ClBr to give [Au(CH2)2PPH2]2(CH2Cl)Br, (2), and the X-ray structure of (2), shows a close contact between one Au centre and the Cl of the co-ordinated CH2Cl [2.895(16)Ă]; this interaction is consistent with the observed further oxidative addition of the CH2Cl to form the bridging methylene A-frame complex, and suggests that a carbene intermediate may be involved.

Characterization of the gold(II) dimer [Au(CH2)2PPh2]2(CH2Cl)Br: structural evidence suggesting the formation of a carbene intermediate preceeding A-frame (bridging methylene) formation

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