Self-assembly of planar molecules on a surface can result in the formation of a wide variety of close-packed or porous structures. Two-dimensional porous arrays provide host sites for trapping guest species of suitable size. Here we show that a non-planar guest species (C(60)) can play a more complex role by promoting the growth of a second layer of host molecules (p-terphenyl-3,5,3″,5″-tetracarboxylic acid) above and parallel to the surface so that self-assembly is extended into the third dimension. The addition of guest molecules and the formation of the second layer are co-dependent. Adding a planar guest (coronene) can displace the C(60) and cause reversion to a monolayer arrangement. The system provides an example of a reversible transformation between a planar and a non-planar supramolecular network, an important step towards the controlled self-assembly of functional, three-dimensional, surface-based supramolecular architectures.

The spontaneous ordering of molecules into two-dimensional self-assembled arrays is commonly stabilized by directional intermolecular interactions that may be promoted by the addition of specific chemical side groups to a molecule. In this paper, we show that self-assembly may also be driven by anisotropic interactions that arise from the three-dimensional shape of a complex molecule. We study the molecule mn 12 o 12 (o 2 CCH 3 ) 16 (H 2 o) 4 (mn 12 (acetate) 16 ), which is transferred from solution onto a Au(111) substrate held in ultrahigh vacuum using electrospray deposition (uHV-EsD). The deposited mn 12 (acetate) 16 molecules form filamentary aggregates because of the anisotropic nature of the molecule-molecule and molecule-substrate interactions, as confirmed by molecular dynamics calculations. The fragile mn 12 o 12 core of the mn 12 (acetate) 16 molecule is compatible with the uHV-EsD process, which we demonstrate using near-edge X-ray adsorption fine-structure spectroscopy. uHV-EsD of mn 12 (acetate) 16 onto a surface that has been prepatterned with a hydrogen-bonded supramolecular network provides additional control of lateral organization.

The tiling of surfaces has long attracted the attention of scientists, not only because it is intriguing intrinsically, but also as a way to control the properties of surfaces. However, although random tiling networks are studied increasingly, their degree of randomness (or partial order) has remained notoriously difficult to control, in common with other supramolecular systems. Here we show that the random organization of a two-dimensional supramolecular array of isophthalate tetracarboxylic acids varies with subtle chemical changes in the system. We quantify this variation using an order parameter and reveal a phase behaviour that is consistent with long-standing theoretical studies on random tiling. The balance between order and randomness is driven by small differences in intermolecular interaction energies, which can be related by numerical simulations to the experimentally measured order parameter. Significant variations occur with very small energy differences, which highlights the delicate balance between entropic and energetic effects in complex self-assembly processes.

Single molecule magnets based on the dodecamanganese (III, IV) cluster with two different types of ligand (acetate and benzoate) have been studied on the Au(111) surface. Due to the non-volatile and fragile nature of the molecules, we have used ultra-high vacuum electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. Synchrotron radiation based electron spectroscopy has been used to study the adsorption of the molecules on the Au(111) surface and the effect that this has on the oxidation states of the manganese atoms in the core. In both cases, reduction of the core is observed due to the interaction with the surface, to essentially the same extent despite substantial differences in the size and nature of the ligand shell.

The synthesis, structural and magnetic characterisation of trinuclear manganese cluster, [Mn(3)O(O(2)C-anth)(6)(HOCH(3))(3)] 1 (where O(2)C-anth = 9-anthracenecarboxylate), with crystallographic three-fold (C(3)) symmetry, are described. The cluster was prepared by a carboxylate exchange reaction between HO(2)C-anth and [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)] with concomitant fragmentation of the dodecanuclear Mn core of the starting material to form a trinuclear Mn(3)(μ(3)-O) cluster capped by six carboxylate ligands. Bond valence sum calculations and SQUID magnetometric measurements establish the oxidation states of the metal ions as Mn(II)·2 Mn(III) which are antiferromagnetically coupled.