Six new bacteriochlorins expanding the range of the strong near-infrared (NIR) absorption (Q(y) band) to both shorter and longer wavelengths (similar to 690 to similar to 900 nm) have been synthesized and characterized. The architectures include bacteriochlorin bisimides that have six-membered imide rings spanning the 3,5- and 13,15-macrocycle positions or five-membered imide rings spanning the beta-pyrrolic 2,3- and 12,13-positions. Both bisimide types absorb at significantly longer wavelength than the bacteriochlorin precursors (no fused rings), whereas oxo-groups at the 7- or 7,17-positions shift the Qy band to a new short wavelength limit. Surprisingly, bacteriochlorin bisimides with five-membered beta-pyrrolic-centered imide rings have a Q(y) band closer to that of six-membered bacteriochlorin-monohnides. However, the five-membered bisimides (versus the six-membered bacteriochlorin-monoimides) have significantly enhanced absorption intensity that is paralleled by an,similar to 2-fold higher fluorescence yield (similar to 0.16 vs,similar to 0.07) and longer singlet excited-state lifetime (,similar to 4 ns vs similar to 2 ns). The pliotophysical enhancements derive in part from mixing of the lowest unoccupied frontier molecular orbitals of the five-membered imide ring with those of the bacteriochlorin framework. In general, all of the new bacteriochlorins have lifetimes (1-4 ns) that are sufficiently long for use in molecular-based systems for photochemical applications. excited-state