Molecular inks based on dimethyl sulfoxide, thiourea (TU), and metal salts have been used to form high optoelectronic quality semiconductors and have led to high power conversion efficiencies for solution-processed photovoltaic devices for Cu2ZnSn(S,Se)(4) (CZTS), Cu2Zn(Ge,Sn)(S,Se)(4) (CZGTS), CuIn(S,Se)(2) (CIS), and Cu(In,Ga)(S,Se)(2) (CIGS). However, several metal species of interest, including Ag(I), In(III), Ge(II), and Ge(IV), either have low solubility (requiring dilute inks) or lead to precipitation or gelation. Here, we demonstrate that the combination of N,N-dimethylformamide (DMF) and TU has the remarkable ability to form intermediate-stability acid-base complexes with a wide number of metal chloride Lewis acids (CuCl, AgCl, ZnCl2, InCl3, GaCl3, SnCl4, GeCl4, and SeCl4), to give high-concentration stable molecular inks. Using calorimetry, Raman spectroscopy, and solubility experiments, we reveal the important role of chloride transfer and TU to stabilize metal cations in DMF. Methylation of TU is used to vary the strength of the Lewis basicity and demonstrate that the strength of the TU-metal chloride complex formed after DMF evaporation is critical to prevent volatilization of metal containing species. Further, we formulated a sulfur-free molecular ink which was used to deposit crystalline CuInSe2 without selenization that sustains high quasi-Fermi level splitting under constant illumination. Finally, we demonstrate the ability of the DMF-TU molecular ink chemistry to lead to high-photovoltaic power conversion efficiencies and high-open-circuit voltages for solution-processed CIS and CZGTS with power conversion efficiencies of 13.4% and 11.0% and V-oc/V-oc,V-SQ of 67% and 63%, respectively.