The significance of hydrogen-bonding interactions in the improvement of chemical and physical properties of functional materials related to sustainable energy, gas absorption, catalysis, and pharmaceuticals has gained considerable research attention. In this report, some unprecedented hydrogen bond motifs between the –COOH group and the solvents capable of forming multiple hydrogen bonds with –COOH are studied. The effects of such diverse motifs on the construction of 3D supramolecular architectures of hydrogen bonded host-guest frameworks and their optical properties are elucidated. For this purpose, structural studies on seven solvates, namely, 1a (1:2DMF), 1b (1:2pyridine), 1c (1:2quinoline) and 2a (1:2DMF), 2b (1:2pyridine), 2c (1:2quinoline), 2d (1:1quinoline:2piperidine), of two isomeric pyromellitic diimide hosts 1 and 2 are carried out. Single crystal X-ray diffraction (SCXRD) analyses revealed that solvates 1a, 2a, 2b show 3D non-porous supramolecular host-guest networks whereas solvates 1b, 1c, 2c, 2d show 3D supramolecular host-guest channelled architectures accommodating the guest solvent molecules inside the cavities of different dimensions. Formation of different hydrogen bond motifs, either cyclic/ring (R) or discrete (D) or combination of both, between the –COOH groups of isomeric hosts and the identical guest molecules are analysed by density functional theory (DFT) calculations. Minor differences in the interaction energies of different motifs of isomeric hosts with the same guest suggest that formation of either motif depends on the steric orientations of hosts and other weak host-guest interactions in the crystal lattices. Solid state fluorescence emission properties of solvates 1a, 2a, 2b are found similar to their respective hosts whereas those are different for solvates 1b, 1c, 2c, 2d from their hosts. Along with the diversity of supramolecular synthons, frontier molecular orbital (FMO) analyses of hydrogen bonded model structures explained well the different emission behaviour of solvates. Thermal analyses for the solvates are in good agreement for the association of numbers of guest solvent molecules with both the isomeric hosts. Overall, this research is focused on establishing the phenomena for formation of distinct hydrogen bond patterns between the two similar host-guest binding groups along with the effect of supramolecular states on the photophysical properties of such hydrogen bonded complexes.