Rare Examples of Transition-Metal−Main-Group Metal Heterometallic Metal−Organic Frameworks from Gallium and Indium Dipyrrinato Complexes and Silver Salts: Synthesis and Framework Variability

New main-group metal dipyrrinato complexes [M(4-pyrdpm)3], where M = Ga3+ or In3+ and 4-pyrdpm is the anion
of 5-(4-pyridyl)dipyrrin (4-pyrdpmH), have been synthesized and incorporated into metal−organic frameworks (MOFs)
by reacting the dipyrrinato complexes with silver(I) salts. MOFs formed with AgOTf (OTf = O3SCF3) and AgSbF6
gave frameworks with three-dimensional (10,3) and two-dimensional (6,3) topologies, respectively. In contrast,
AgPF6 produced both (10,3) and (6,3) network topologies, suggesting that the PF6 anion has little preference for
templating (10,3) versus (6,3) frameworks within this system. These findings update an earlier MOF study that
examined the role of these anions in templating related heterometallic MOFs which used [Fe(4-pyrdpm)3] and
[Co(4-pyrdpm)3] metalloligands. All of the dipyrrin compounds reported here have been characterized by single-crystal X-ray crystallography, including the first crystallographically characterized example of a 1,2,3-unsubstituted
free-base dipyrrin, 4-pyrdpmH.