Capping TTFtt enables facile transmetalation in three different oxidation states.
Organic diradicals are uncommon species that have been intensely studied for their unique properties and potential applicability in a diverse range of innovative fields. While there is a growing class of stable and well characterized organic diradicals, there has been recent focus on how diradical character can be controlled or modulated with external stimuli. Here we demonstrate that a diiron complex bridged by the doubly oxidized ligand tetrathiafulvalene-2,3,6,7tetrathiolate (TTFtt 2−) undergoes a thermally induced Fe-centered spin-crossover which yields significant diradical character on TTFtt 2−. UV-vis-Near-IR, Mössbauer, NMR, and EPR spectroscopies with magnetometry, crystallography, and advanced theoretical treatments suggest that this diradical character arises from a shrinking TTFtt 2− π-manifold from the Fe(II)-centered spin-crossover. The TTFtt 2− centered diradical is predicted to have a singlet ground state by theory and variable temperature EPR. This unusual phenomenon demonstrates that inorganic spin transitions can be used to modulate organic diradical character. Results and Discussion Synthesis and Structural Parameters Complex 1 was synthesized via reaction with the deprotected proligand 2,3,6,7-tetrakis(2cyanoethylthio)tetrathiafulvalene (TTFtt(C2H4CN)4) in good yield. Complex 1 was insoluble in all solvents we investigated which precluded detailed characterization but is pure as indicated by combustion analysis and behaves as a suitable synthon for subsequent chemistry. Complex 1 can be doubly oxidized with [Cp2Fe][BAr F 4] to form 2 which is more soluble, enabling common solution characterization including 1 H NMR and cyclic voltammetry measurements (Figure S1-S2). Oxidation from 1 to 2 could be ligandcentered (TTFtt 4− →TTFtt 2−), metal-centered (2 Fe(II)→2 Fe(III)), or some intermediate case, but the data acquired for 2 supports a TTFtt 2− structure arising from ligandcentered oxidation (Chart 1B, see below). Compound 2 was structurally characterized via singlecrystal X-ray diffraction (SXRD) at 293 K (2-HT; Figure S3) and 100 K (2-LT; Figure 1). In both structures TTFtt 2− is bridged between two TPA-capped Fe centers with two outer-sphere BAr F 4 − counter anions. The most striking difference between these temperatures is markedly longer Fe bond lengths in 2-HT. The Fe-Npyridine and Fe-Namine bond lengths in 2-LT are 1.958(6)-1.979(6) and 2.017(6) Å (Figure 1), respectively. These values are consistent with Fe-N bonds in other low-spin complexes with a Fe-TPA moiety. 16,17 In 2-HT, these bonds are 0.18-0.19 and 0.244(11) Å longer than their counterparts at 100 K, respectively, and are consistent with high-spin Fe-TPA complexes. The shorter Fe bonds at lower temperature indicate that 2 exhibits a temperature dependent spincrossover as observed in related compounds. 16,21
ParagraphConducting organic materials, such as doped organic polymers, 1 molecular conductors, 2, 3 and emerging coordination polymers, 4 underpin technologies ranging from displays to flexible electronics. 5 Realizing high electrical conductivity in traditionally insulating organic materials necessitates tuning their electronic structure through chemical doping. 6 Furthermore, even materials that are intrinsically conductive, such as single-component molecular conductors, 7,8 require crystallinity for metallic behavior. However, commercial conducting polymers are often purposefully amorphous to aid in durability and processability. 9,10 Using molecular design to engender high conductivity in undoped amorphous materials would enable tunable and robust conductivity in many applications, but there are no intrinsically conducting organic materials which maintain high conductivity when disordered. Here we show that the completely amorphous coordination polymer Ni tetrathiafulvalene tetrathiolate (NiTTFtt) displays intrinsic metallic conductivity. Despite its disordered structure, NiTTFtt exhibits remarkably high electronic conductivity (1280 S/cm) and intrinsically glassy metallic behavior. Analysis with advanced theory shows that these properties are enabled by strong molecular overlap and correlation that are robust to structural perturbations. This unusual set of structural and electronic features results in remarkably stable organic conductivity which is maintained in air for weeks and at temperatures up to 140 °C. Our results demonstrate that molecular design can enable metallic conductivity even in heavily disordered materials. This both raises fundamental questions about how band-like transport can exist in the absence of periodic structure as well as suggests exciting new applications for these materials.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.