The tridentate organic ligand 4,4′,4′′-(4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-2,6,10-triyl)tribenzoic acid (H3L) has been synthesized (as the methanol 1.25-solvate, C48H39NO6·1.25CH3OH). As a donor–acceptor motif molecule, H3L possess strong intramolecular charge transfer (ICT) fluorescence. Through hydrogen bonds, H3L molecules construct a two-dimensional (2D) network, which pack together into three-dimensional (3D) networks with an ABC stacking pattern in the crystalline state. Based on H3L and M(NO3)2 salts (M = Cd and Zn) under solvothermal conditions, two metal–organic frameworks (MOFs), namely, catena-poly[[triaquacadmium(II)]-μ-10-(4-carboxyphenyl)-4,4′-(4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-2,6-diyl)dibenzoato], [Cd(C48H37NO6)(H2O)3]
n
, I, and poly[[μ3-4,4′,4′′-(4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-2,6,10-triyl)tribenzoato](μ3-hydroxido)zinc(II)], [Zn2(C48H36NO6)(OH)]
n
, II, were synthesized. Single-crystal analysis revealed that both MOFs adopt a 3D structure. In I, partly deprotonated HL
2− behaves as a bidentate ligand to link a CdII ion to form a one-dimensional chain. In the solid state of I, the existence of weak interactions, such as O—H...O hydrogen bonds and π–π interactions, plays an essential role in aligning 2D nets and 3D networks with AB packing patterns for I. The deprotonated ligand L
3− in II is utilized as a tridentate building block to bind ZnII ions to construct 3D networks, where unusual Zn4O14 clusters act as connection nodes. As a donor–acceptor molecule, H3L exhibits fluorescence with a photoluminescence quantum yield (PLQY) of 70% in the solid state. In comparison, the PL of both MOFs is red-shifted with even higher PLQYs of 79 and 85% for I and II, respectively.
PAH/PAH(CF
3
)
n
Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals
