Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Abstract

The research into adamantane-type compounds has gained momentum in recent years, yielding remarkable new applications for this class of materials. In particular, organic adamantane derivatives (AdR₄) or inorganic adamantane-type compounds of the general formula [(RT)₄E₆] (R: organic substituent; T: group 14 atom C, Si, Ge, Sn; E: chalcogenide atom S, Se, Te, or CH₂) were shown to exhibit strong nonlinear optical (NLO) properties, either second-harmonic generation (SHG) or an unprecedented type of highly-directed white-light generation (WLG) – depending on their respective crystalline or amorphous nature. The (missing) crystallinity, as well as the maximum wavelengths of the optical transitions, are controlled by the clusters' elemental composition and by the nature of the organic groups R. Very recently, it has been additionally shown that cluster cores with increased inhomogeneity, like the one in compounds [RSi{CH₂Sn(E)R′}₃], not only affect the chemical properties, such as increased robustness and reversible melting behaviour, but that such ‘cluster glasses’ form a conceptually new basis for their use in light conversion devices. These findings are likely only the tip of the iceberg, as beside elemental combinations including group 14 and group 16 elements, many more adamantane-type clusters (on the one hand) and related architectures representing extensions of adamantane-type clusters (on the other hand) are known, but have not yet been addressed in terms of their opto-electronic properties. In this review, we therefore present a survey of all known classes of adanmantane-type compounds and their respective synthetic access as well as their optical properties, if reported.