Case Studies in Nanocluster Synthesis and Characterization: Challenges and Opportunities.

Atomically precise nanoclusters (APNCs) are an emerging area of nanoscience. Their monodispersity and well-defined arrangement of capping ligands facilitates the interrogation of their fundamental physical properties, allowing for the development of structure-function relationships, as well as their optimization for a variety of applications, including quantum computing, solid-state memory, catalysis, sensing, and imaging. However, APNCs present several unique synthetic and characterization challenges. For example, nanocluster syntheses are infamously low yielding and often generate complicated mixtures. This combination of factors makes nanocluster purification and characterization more difficult than that of typical inorganic or organometallic complexes. Yet, while this fact is undoubtedly true, the past lessons learned from the characterization of inorganic complexes are still useful today. In this Account, we discuss six case studies taken from the recent literature in an attempt to identify common challenges and pitfalls encountered in APNC synthesis and characterization. For example, we show that several reducing agents employed in APNC synthesis, including the commonly used reagent NaBH4, do not always behave as anticipated. Indeed, we highlight one case where NaBH4 reduces the ligand and not the metal center, and other cases where NaBH4 acts as a Brønstead base instead of a reducing agent. In addition, we have identified several instances where the use of phase transfer agents, which were added to mediate APNC formation, played no role in the nanocluster synthesis, and likely made the isolation of pure material more difficult. We have also identified several cases of cluster misidentification driven by spurious or ambiguous characterization data, most commonly collected by mass spectrometry. To address these challenges, we propose that the nanocluster community adopt a standard protocol of characterization, similar to those used by the organometallic and coordination chemistry communities. This protocol requires that many complementary techniques be used in concert to confirm formulation, structure, and analytical purity of APNC samples. Two techniques that are underutilized in this regard are combustion analysis and NMR spectroscopy. NMR spectroscopy, in particular, can provide information on purity and formulation that are difficult to collect with any other technique. X-ray absorption spectroscopy is another powerful method of nanocluster characterization, especially in cases where single crystals for X-ray diffraction are not forthcoming. Chromatographic techniques can also be extremely valuable for assessing purity, but are rarely used during APNC characterization. Our goal with this Account is to begin a discussion with respect to the best protocols for nanocluster synthesis and characterization. We believe that embracing a standard characterization protocol would make APNC synthesis more reliable, thereby accelerating their integration into a variety of technologies.