Four diplatinum(II) complexes with the formula [Pt(pypm)(mu-F-n)](2) (2, 3a-c) bearing both a pyridine-pyrimidinate chelate and formamidinate bridge, where (pypm)H and (FH)-H-n stand for 5-(pyridin-2-yl)-2-(trifluoromethyl)pyrimidine and functional formamidines with various substituents of Pr-i (n = 1), Ph (n = 2), (C6H4Bu)-Bu-t (n = 3), and C6H4CF3 (n = 4), were synthesized en route from a mononuclear intermediate represented by [Pt(pypm)Cl-((FH)-H-1)] (1). Single-crystal X-ray diffraction studies confirmed the structure of 1 and 3a comprised of an individual "Pt(pypm)" unit and two "Pt(pypm)" units with a Pt center dot center dot center dot Pt distance of 2.8845(2) angstrom, respectively. Therefore, in contrast to the structured emission of mononuclear 1 with the first vibronic peak wavelength at 475 nm, all other diplatinum complexes with shortened Pt center dot center dot center dot Pt separation exhibited greatly red shifted and structureless metal-metal to ligand charge transfer (MMLCT) emission that extended into the near-infrared region in solid states. Their photophysical characteristics were measured under three distinctive morphological states (i.e., crystals, sublimed powders, and vacuum-deposited thin films) by steady-state UV-vis spectroscopy, while retention of Pt center dot center dot center dot Pt interactions in deposited thin films of 2 and 3a-c was confirmed using Raman spectroscopy, demonstrating lowered Pt center dot center dot center dot Pt stretching at 80-200 cm(-1). Most importantly, complexes 3a-c exhibited a gradual red shift with the trends crystals < sublimed powders < vacuum-deposited thin films, a result of increased intermolecular pi-pi stacking interactions and Pt center dot center dot center dot Pt interactions, while crystalline samples exhibited the highest luminescence among all three morphological states due to the fewest defects in comparison to other morphologies. Finally, 3b was selected as a nondoped emitter for the fabrication of NIR-emitting OLEDs, giving an electroluminescence peak at 767 nm and a maximum external quantum efficiency of 0.14% with negligible roll-off.