ABSTRACT: The optoelectronic properties of covalent organic frameworks (COFs) can be controlled by the design of their molecular building blocks and assembly. Here, a facile and efficient synthetic route is reported for the novel thiophene-enriched tetrathienonaphthalene (TTN)-based node 4,4',4″,4'″-(naphtho[1,2-b:4,3-b':5,6-b″:8,7-b″']tetrathiophene-2,5,8,11-tetrayl)tetraaniline (TTNTA) for constructing imine-linked COFs. Utilizing TTNTA, highly crystalline, thiophene-enriched donor-donor (D-D) and donor-acceptor (D-A) COFs, denoted as TT COF and BDT(BT)2 COF, are synthesized using two distinct aldehyde-functionalized linear linkers: [2,2'-bithiophene]-5,5'-dicarbaldehyde (TT) and 7,7'-(4,8-diethoxybenzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(benzo[c][1,2,5]thiadiazole-4-carbaldehyde) (BD
