Six new platinum(H) chloride complexes 1-6 containing a 6-[9-di(2-ethylhexyl)-7-R-9H-fluoren-2-yl]-2,2'-bipyridine (R = NO2, CHO, benzothiazol-2-yl (BTZ), n-Bu, carbazol-9-yl (CBZ), NPh2) ligand were synthesized and characterized. The influence of the electron-donating or electron-withdrawing substituent at the 7-position of the 8 fluorenyl component on the photophysics of these complexes was systematically investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). Electron-withdrawing or -donating substituents exert distinct effects on the photophysics of the complexes. All complexes feature a low-energy, broad (MLCT)-M-1 (metal-to-ligand charge transfer)/(ILCT)-I-1 (intraligand charge transfer)/(1)pi,pi* absorption band (tail) above ca. 430 nm and a major. absorption band(s) between 320 and 430 nm, which admix (MLCT)-M-1, 1 pi,pi*, (1)ILCTand/or (LLCT)-L-1 (ligand-to-ligand charge transfer) characters. The contributions of different configurations to the major absorption band(s) vary depending on the nature of the substituent. Strong electron-donating or -withdrawing substituents (NPh2 and NO2) and the aromatic substituent BTZ cause a pronounced red-shift of the absorption spectra of 1, 3, and 6. All complexes are emissive at room temperature and at 77 K. The emitting, excited state is dominated by (3)pi,pi* character in 1-3, with some contributions from (MLCT)-M-3 in 1 and 2, while the emission is predominantly from the (MLCT)-M-3 state for 4 and 5 but with some (3)pi,pi* character. For 6, the emitting state is (ILCT)-I-3 in nature. With the increased electron-donating ability of the substituent, the (3)pi,pi* character, diminishes while charge transfer character increases. All complexes exhibit broad and strong triplet excited-state absorption (TA) from the near-UV to the near-IR spectral region. The TA band maxima are red-shifted for complexes 1-3 (which possess the electron-withdrawing substituents) compared to those of 4-6 (which contain electron-donating substituents). All complexes manifest strong reverse saturable absorption (RSA) for a nanosecond laser pulse at 532 nm, which originates from the much stronger triplet excited-state absorption than the ground-state absorption of 1-6 in the visible spectral region. The strength of RSA follows this trend: 4 approximate to 5 < 1 approximate to 3 < 2 <6, which is primarily determined by the ratio of the triplet excited-state absorption cross section relative to that of the ground-state absorption (sigma(ex)/sigma(0)) at 532 nm. The sigma(ex)/sigma(0) ratios (116-261) of 1-6 at 532 nm are much larger than those of most of the reverse saturable absorbers reported in the literature, with the ratio of 6 (sigma(ex)/sigma(0) = 261) being among the largest values reported to date. This makes complexes 1-6, especially 6, very promising reverse saturable absorbers.