The application of supramolecular chemistry on solid surfaces represents an exciting field of research that continues to develop in new and unexpected directions. This review highlights recent advances in the field which range from the fundamental aspects of the thermodynamics of self-assembly through to the development of new materials with potential application as new materials. The unique aspects of working on solid surfaces are highlighted and advances in the assembly of many component systems and highly complex fractal-like and quasicrystalline systems discussed. The unique features of working in the surface-based environment and the utilisation of scanning probe microscopies as a primary characterisation tool are highlighted.

Varying the degree of thionation of a series of naphthalene diimide (NDI) and naphthalic imide (NI) phenothiazine dyad systems affords a systematic approach for tuning the system's donor-acceptor energy gap. Each dyad was compared to model NDI/NI systems and fully characterised through single crystal X-ray diffraction, NMR, cyclic voltammetry, electron paramagnetic resonance (EPR), transient absorption spectroscopy (TA), time-resolved infra-red spectroscopy (TRIR) and DFT. The measurements reveal that thionation increases both electron affinity of the NDI/NI acceptor dyad component and accessibility of the singly or doubly reduced states. Furthermore, FTIR and TA measurements show that excited state behaviour is greatly affected by thionation of the NDI and induces a decrease in the lifetime of the excited states formed upon the creation of charge-separated states.

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The self-assembly of supramolecular arrays at solid surfaces is discussed with an emphasis on the degree of complexity that can be generated in such structures. The preparation of multi-component arrays is reviewed illustrating the approaches to generating many-component networks and the challenges that are encountered. The complexity of quasicrystalline and fractal molecular structures is also demonstrated along with recent developments in the synthesis of complexity perpendicular to the solid substrate through the formation of bilayer structures. Overall the importance of characterisation by scanning probe microscopy is evident in determining the complexity of structures at the molecular level.

Mechanically interlocked molecules that employ a handcuff component provide a pathway to highly unusual structures, a new nomenclature is proposed which helps to identify opportunities for employing this structural unit for new architectures.