Despite the traditional plasmonic materials are counted on one hand, there are a lot of possible combinations leading to alloys with other elements of the periodic table, in particular those renowned for magnetic or catalytic properties. It is not a surprise, therefore, that nanoalloys are considered for their ability to open new perspectives in the panorama of plasmonics, representing a leading research sector nowadays. This is demonstrated by a long list of studies describing multiple applications of nanoalloys in photonics, photocatalysis, sensing and magneto‐optics, where plasmons are combined with other physical and chemical phenomena. In some remarkable cases, the amplification of the conventional properties and even new effects emerged. However, this field is still in its infancy and several challenges must be overcome, starting with the synthesis (control of composition, crystalline order, size, processability, achievement of metastable phases and disordered compounds) as well as the modelling of the structure and properties (accuracy of results, reliability of structural predictions, description of disordered phases, evolution over time) of nanoalloys. To foster the research on plasmonic nanoalloys, here we provide an overview of the most recent results and developments in the field, organized according to synthetic strategies, modelling approaches, dominant properties and reported applications. Considering the several plasmonic nanoalloys under development as well as the large number of those still awaiting synthesis, modelling, properties assessment and technological exploitation, we expect a great impact on the forthcoming solutions for sustainability, ultrasensitive and accurate detection, information processing and many other fields.

Several examples of nanosized therapeutic and imaging agents have been proposed to date, yet for most of them there is a low chance of clinical translation due to long-term in vivo retention and toxicity risks. The realization of nano-agents that can be removed from the body after use remains thus a great challenge. Here, we demonstrate that non-equilibrium gold-iron alloys behave as shape-morphing nanocrystals with the properties of self-degradable multifunctional nanomedicines. DFT calculations combined with mixing enthalpy-weighted alloying simulations predict that Au-Fe solid solutions can exhibit self-degradation in aqueous environment if the Fe content exceeds a threshold that depends upon element topology in the nanocrystals. Exploiting a laser-assisted synthesis route, we experimentally confirm that non-equilibrium Au-Fe nanoalloys have a 4D behavior, that is the ability to change shape, size and structure over time, becoming ultrasmall Au-rich nanocrystals. In vivo tests show the potential of these transformable Au-Fe nanoalloys as efficient multimodal contrast agents for magnetic resonance imaging and computed x-ray absorption tomography and further demonstrate their self-degradation over time, with a significant reduction of long-term accumulation in the body, when compared to benchmark gold or iron oxide contrast agents. Hence, Au-Fe alloy nanoparticles exhibiting 4D behavior can respond to the need for safe and degradable inorganic multifunctional nanomedicines required in clinical translation.