A series of 2D metals, β-(BDT-TTP)6[Re6Se 6Cl8]·(CHCl2-CHCl2) 2, 2; β-(ST-TTP)6[Re6S6Cl 8]·(CH2-Cl-CHCl2)2, 3; β-(BDT-TTP)7[Re6S6Cl8] 0.5[Re6S7Cl7] 0.5·(CH2Cl2), 4; β-(BDT-TTP) 7[Re6Se6Cl8]0.5[Re 6S7-Cl7]0.5·(CH 2Cl2), 5; β-(BDT-TTP)8[Re 6S7Cl7]·(CH2Cl 2)4, 6 (BDT-TTP and ST-TTP are 2,5-bis(1,3-dithiol-2- ylidene)-1,3,4,6-tetrathiapentalene and 2-(1,3-diselenol-2-ylidene)-5(1,3- dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene, respectively) is reported to have one single β-slab layered topology despite successive increases of the cluster anion negative charge. The charge density within the templating composite inorganic-neutral molecule slab is shown to remain above a threshold of ca. one negative charge per square nanometer, that is, for cluster anions with two negative charges and higher. Conversely, discrete stacks are shown to be stabilized instead in the semiconducting salts (BDT-TTP)2[Re 6S5Cl9], 1 where the cluster anion bears one negative charge only. The electronic structure of salts 2-6 is shown to be very stable and kept almost intact across the series. The templating strategy is shown to fulfill its anticipated potential for deliberate installment of incommensurate band fillings in molecular metals. The deliberate admixture of the 6:1 and 8:1 structures yields novel phases with a 7:1 stoichiometry with the anticipated crystal and electronic structures. The action at the organic-inorganic interface triggered by changing the anion charge yet keeping its shape and volume identical, which ultimately governs the shape of the unit cell, is of paramount importance in defining the Fermi surface of these metallic salts. The present BDT-TTP salts thus provide a series of materials with strongly related but subtly different Fermi surfaces worthy of many physical studies. Shubnikov-de Haas measurements are expected to be particularly interesting since they are especially sensitive to the details of the Fermi surface. © 2008 American Chemical Society.