Organic moieties with low-lying empty pi-orbitals often act as acceptors in pi-conjugated materials and can affect ground- and excited state characteristics such as the wavelengths of light absorption and emission, electron affinity (EA), and ionization energy (IE), which are often key properties for applications including non-linear optics, organic photovoltaics, and organic field-effect transistors. However, incorporation of strong π-acceptors into either small molecule or polymer materials, which is typically performed via Stille or Suzuki catalytic aryl-aryl couplings, can be problematic since many high-EA precursors are resistant to electrophilic halogenation, lithiated derivatives typically used to form Stille and Suzuki reagents are often unstable, and typically—even if the corresponding Stille or Suzuki reagents can be synthesized—they are relatively poor coupling partners. This low reactivity often requires harsh reaction conditions and leads to low reaction yields. Incorporation of more electron-rich “handles”, such as thiophene groups onto the core of an electron accepting unit can help address these problems, but can limit the structural variation achievable and limit the extent to which EA and IE can be increased. Direct C-H bond functionalization on sp3 and sp2 carbon centers has been applied previously to interesting synthetic challenges in pharmaceutical and natural product synthesis. More recently, direct C-H arylation has become a useful tool for the synthesis of pi-conjugated small molecules and polymers. Potentially, direct C-H arylation can be particularly useful in the synthesis of materials with high EA, where it may be used to circumvent some of the synthetic difficulties associated with strongly electron-accepting intermediates and with conventional cross-coupling partners. To assist in exploring the scope of direct C-H arylation of high EA materials, we have synthesized several heterocycles based on widely used 2,1,3-benzothiadiazole (BT), benzotriazole (BTz), and quinoxaline (Qx) acceptors with pendant electron withdrawing substituents to increase EA relative to the parent acceptors. Palladium-catalyzed direct heteroarylation of 5,6-dicyano[2,1,3]benzothiadiazole (DCBT), 5,6-dicyano[1,2,3]benztriazole (DCBTz), 6,7-dicyanoquinoxaline (DCQx), and 6,7-dinitroquinoxaline (DNQx) was accomplished with high yields (>80%) of di-coupled products in most cases. In some cases, the C-H activated arylation was sufficiently high yielding for the synthesis of of donor-acceptor (D-A) polymers with average number molecular weight greater than 20 kDa, although polymerization with thiophene donor monomers suffered from deleterious side reactions. Small molecule thiophene derivatives of the DCBT, DCBTz, and DCQx acceptors were prepared and compared to analogous derivatives of BT and BTz parent acceptors to demonstrate the comparatively high EA of DCBT, DCBTz, and DCQx, which were in close agreement with quantum chemical calculations. The generally high yields of the cross-coupling reactions of the high EA building blocks described herein show that direct C-H arylation is a potentially useful general approach to the incorporation of strong electron acceptors into pi-conjugated small molecules and polymers. In particular, the use of direct C-H arylation has the potential to effectively turn the persistent synthetic limitations associated with high EA substrates into a synthetic strength.