Lowering the charge of Zintl anions by (element-)organic substituents allows their use as sources of (semi)metal nanostructures in common organic solvents, as realized for group 15 anions or Ge 9 4 and Sn 9 4. We developed a new strategy for other anions, using low-coordinate 3d metal complexes as electrophiles. [K(crypt-222)] + salts of (TrBi 3) 2 anions dissolved in situ in Et 2 O and/or THF when reacted with [Mn(hmds) 2 ]. Work-up afforded soluble [K(crypt-222)] + salts of [{(hmds) 2 Mn} 2 (TlBi 3)] 2 (in 1), [{(hmds) 2 Mn} 2-(Bi 2)] 2 (in 2), and [{(hmds)Mn} 4 (Bi 2) 2 ] 2 (in 3) (crypt-222 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8.8.8]hexacosane; Tr = Ga, In, Tl; hmds = N(SiMe 3) 2), representing rare cases of Zintl clusters with open-shell metal atoms. 1 comprises the first coordination compound of the (TlBi 3) 2 anion, 2 features a diamondshaped {Pn 2 M 2 } unit, and 3 is a mixed-valent Mn I /Mn II compound. The uncommon electronic structures in 1-3 and magnetic coupling were studied by comprehensive DFT calculations.