1,3-Benzenedithiol (BDTH2) (Figure ) has the same number of carbons between the two -SH groups as PDTH2, albeit in the form of a rigid benzene group. However, exchange reactions conducted with BDTH2 at both room temperature and 60 °C failed to produce homologues of 4, such as [Au24Pt(TBBT)12(BDT)3] 0 (Scheme S9 and Figure ), even when the BDTH2 concentration was varied and the reaction time was increased. This outcome underscores the importance of optimizing both the length and flexibility of the carbon chain to enable the precise synthesis of dithiolate-containing NCs, such as 3 or 4.