Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions, (0-TP)n- (n = 2-100), (m-TP) n- (n = 2-100), and (p-TP)n- (n = 1-100), respectively, are conducted to investigate the effect of molecular shape on the molecular aggregation form and the resultant ion core character of the clusters. For (o-TP)n- and (m-TP)n-, neither magic numbers nor discernible isomers are observed throughout the size range. Furthermore, their vertical detachment energies (VDEs) increase up to large n and depend linearly on n-1/3, implying that they possess a three-dimensional (3D), highly reorganized structure encompassing a monomelic anion core. For (p-TP)n-, in contrast, prominent magic numbers of n = 5, 7, 10, 12, and 14 are observed, and the VDEs show pronounced irregular shifts below n = 10, while they remain constant above n = 14 (isomer A). These results can be rationalized with two-dimensional (2D) orderings of p-TP molecules and different types of 2D shell closure at n = 7 and 14, the monomelic and multimeric anion core, respectively. Above n = 16, the new feature (isomer B) starts to appear at the higher binding side of isomer A, and it becomes dominant with n, while isomer A gradually disappears for larger sizes. In contrast to isomer A, the VDEs of isomer B continuously increase with the cluster size. This characteristic size evolution suggests that the transition to modified 2D aggregation forms from 2D ones occurs at around n = 20.
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