Design and Applications of Single-Component Radical Conductors

Pancake Bonding Seen through the Eyes of Spectroscopy

“…Te⋯Te) of 3 are much weaker in strength and have a positive (destabilizing) energy density value H b at the Te⋯Te bond critical point r b revealing that the Te⋯Te do not have a typical pancake bond nature as we observed 1 and 2. [7] All pancake bonding interactions within the phenalenyl dimer (4), 2,5,8trimethylphenalenyldimer (5), and the 2,5,8-tri-t-butylphenalenyl dimer (6) were observed to have postive (destabilizing) H b values revealing that their pancake interactions are electrostatic in nature. [8] From BSO n(CC) values, the calculated AI, and related WS and ALT parameters we found that the dimerization of phenalenyl-based monomers leads to an increased aromaticity primarily due to CC bond strengthening.…”

“…Such interactions have received a considerable amount of interest as they allow one to synthesize novel radical-based materials, via electron or hole through-space delocalization, that exhibit unique magnetic [5], optical [6], and electronic properties (i.e. conductive polymers, organic conductors) [7].…”

Design of an n-type low glass transition temperature radical polymer

“…In fact, the initial intrigue and evaluation of radical polymers came about due to the rapid redox reactions involved with their pendant groups; as such, most of the application focus of these materials was centered on electrolyte-based systems. [7][8][9][10] Thus, radical polymers were frequently utilized in energy storage applications due to the high density of redoxactive species present along the pendant groups of the macromolecules. [9][10][11][12][13][14][15][16][17][18][19][20][21][22] Whereas, only over the last handful of years have the solid-state electrical conductivity properties of radical polymers been evaluated in full.…”

“…[9][10][11][12][13][14][15][16][17][18][19][20][21][22] Whereas, only over the last handful of years have the solid-state electrical conductivity properties of radical polymers been evaluated in full. 8,[23][24][25][26][27][28] In many of the early solid-state electrical conductivity evaluation efforts, the conductivity of a model radical polymer, poly (2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA), was quantified by multiple groups with the a highest value of ∼10 −4 S m −1 being reported. 23,26,29,30 This solid-state electrical conductivity was improved due to an improved radical polymer design in that poly(2,3-bis(2′,2′,6′,6′-tetramethylpiperidinyl-Noxyl-4′-oxycarbonyl)-5-norbornene) (PTNB) had a higher radical content than what was typically observed in the PTMAbased macromolecular design case, and a thin film of this material achieved a solid-state electronic conductivity of 7 × 10 −3 S m −1 .…”

“…[38][39][40][41][42][43][44][45][46][47] This draws a parallel to the conjugated polymer literature where hole-transporting macromolecules dominated the research landscape; however, it was clear in the conjugated polymer regime previously, and it is clear in the radical polymer community now, that developing preferentially-reduced (i.e., n-type) open-shell macromolecules will be of critical importance in the near future. 3,8,48,49 To address this gap, here we design, synthesize, and characterize the electronic and electrochemical properties of the first low glass transition temperature, n-type (i.e., preferentiallyreduced) radical polymer. Specifically, we synthesized a radical polymer with a flexible polysiloxane backbone bearing galvinoxyl radical moieties, poly [2,6-…”