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As an electron-deficient element, boron possesses fascinating three-dimensional structures and unconventional chemical bonds. Nanoclusters of boron have also been found to exhibit intriguing structural properties, observed to have predominantly planar structures, in stark contrast to bulk boron allotropes, which are composed of the ubiquitous B₁₂icosahedral building blocks. Here, we report observation of the 2D-to-3D transition and bulk-like structural features in the size-selected boron clusters, as revealed by photoelectron spectroscopy, chemisorption experiments, and first-principles calculations. In the small to medium cluster size range, planar boron cluster anions are found to be unreactive and only B₄₆^–and B₅₆^–are observed to chemisorb C₂H₄and CO under ambient conditions, suggesting major structural transitions at these cluster sizes. Notably, B₅₆^–is also found to be able to chemisorb and activate CO₂. The global minimum of B₄₆^–is found to adopt a core-shell structure (B₂@B₄₄^–), consisting of a B₂core within a B₄₄shell, reminiscent of the interstitial B₂dumbbells in the high-pressureγ-B₂₈form of bulk boron. More remarkably, both the global minimum and the second most stable isomer of B₅₆^–exhibit nest-like configurations, featuring the iconic B₁₂icosahedral core surrounded by a B₄₄half-shell (B₁₂@h-B₄₄^–), signifying the onset of bulk-like structural characteristics in boron nanoclusters. 

A seventh blind test of crystal structure prediction was organized by the Cambridge Crystallographic Data Centre featuring seven target systems of varying complexity: a silicon and iodine-containing molecule, a copper coordination complex, a near-rigid molecule, a cocrystal, a polymorphic small agrochemical, a highly flexible polymorphic drug candidate, and a polymorphic morpholine salt. In this first of two parts focusing on structure generation methods, many crystal structure prediction (CSP) methods performed well for the small but flexible agrochemical compound, successfully reproducing the experimentally observed crystal structures, while few groups were successful for the systems of higher complexity. A powder X-ray diffraction (PXRD) assisted exercise demonstrated the use of CSP in successfully determining a crystal structure from a low-quality PXRD pattern. The use of CSP in the prediction of likely cocrystal stoichiometry was also explored, demonstrating multiple possible approaches. Crystallographic disorder emerged as an important theme throughout the test as both a challenge for analysis and a major achievement where two groups blindly predicted the existence of disorder for the first time. Additionally, large-scale comparisons of the sets of predicted crystal structures also showed that some methods yield sets that largely contain the same crystal structures.