Using the rules defining the SG of outstanding oxygenate production for the three-component data, we designed more complex materials containing additional elements. We start by considering four-component materials containing ruthenium, tungsten, phosphorus, and one additional V Ç element. For this analysis, we fix the phosphorus content to 0.60 according to the rule identified in Fig. . To further reduce the number of possible variables determining the catalyst composition, we also fix the ruthenium molar content to 0.05. We focus on such relatively low ruthenium loadings to ensure that the formation of combustion products is not significant. In this way, the compositions of the four-component materials are determined solely by the choice of V Ç element and its molar content. Materials with V Ç molar content of 0.35, which do not contain tungsten and are thus composed by three elements, are also referred to as four-component materials in our analysis to highlight that they contain different chemical elements compared to ruthenium, tungsten and phosphorus, the elements used to derive the rules. We concentrate on V Ç elements that show octahedral coordination patterns among reported phosphorus-containing materials structures and that have a maximum atomic radius difference compared to tungsten of 0.10 Å (see details in ESI). This is to ensure that only elements that are compatible with tungsten, i.e., that could possibly replace tungsten in the material structure, are taken into account. The following V Ç are considered: niobium, tantalum, chromium, molybdenum, tin, antimony, and tellurium. These elements have atomic radii of 1.45, 1.45, 1.40, 1.45, 1.45, 1.45, and 1.40 Å, respectively. The atomic radius of tungsten is 1.45 Å. We have also included lead in this analysis, since materials containing this element were also experimentally tested (see below). ). The oxygenate yields shown in C correspond to materials with J É = 0.035 for the cases V ^= Mo, Nb, and with J É = 0.050 for the cases V ^= Ta, Sb. The white cells in C indicate materials not measured by HTE. We evaluated the composition-averaged electronegativity (VY) for the selected V Ç and the molar contents 0.05, 0.175, 0.30 and 0.35 in Fig. . In this figure, the VY values for the new fourcomponent materials are shown in bold and marked with starts if they satisfy the SG rule 3.910 ≤ VY < 4.002 eV. This catalyst map suggests that the use of 5.0 to 17.5 % (molar) of niobium, chromium, molybdenum, tin, lead and antimony, in the catalyst composition in addition to ruthenium, tungsten and phosphorus, results in catalysts which are part of the identified SG, and thus likely high-performant materials. For the case of tantalum and tellurium, 17.5 % (molar) or more of these elements is needed for the resulting materials to present the VY values compatible with the SG. The four-component catalyst compositions shown in Fig. were tested in propylene oxidation using HTE at the same reaction conditions compared to those used for testing the threecomponent materials. The highest yield of oxygenates achieved for each composition is shown by the colors in Fig. . The comparison of the experimental results with the SG rules on VY shows that the catalyst design rules derived by SGD correctly describe the experimental trend. In particular, the materials based on niobium, chromium, molybdenum, tin, lead and antimony achieve the highest oxygenate yields at relative lower V Ç molar fractions compared to the tantalum and telluriumbased materials, in line with the optimal ranges of VY values indicated by the SG rules.