One co-crystal structure characterized to identify and quantify various non-covalent interactions with spectroscopy, X-ray crystallography and density functional theory computations.

Small molecular organic fluorophores have garnered significant interest because of their indispensable use in fluorescence imaging (FI) and optoelectronic devices. Herein, we designed triphenylamine (TPA)-capped donor− acceptor−donor (D−A−D)-based fluorophores having a variation at the heterocyclic donor (D) units, 3,4-ethylenedioxythiophene (EDOT), furan (FURAN), thiophene (THIO), and 1-methyl-1H-pyrrole (MePyr), with isoindigo as the core electron acceptor (A) unit. Synthesis of these fluorophores (II-X-TPA) resulted in four symmetrical dye molecules: II-EDOT-TPA, II-FURAN-TPA, II-THIO-TPA, and II-MePyr-TPA, where TPA functioned as a terminal unit and a secondary electron donor group. Photophysical, electrochemical, and computational analyses were conducted to investigate the effect of heterocyclic donor units on the II-X-TPA derivatives. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations provided insightful features of structural and electronic properties of each fluorophore and correlated well with experimental observations. Electron density distribution maps, overlapping frontier molecular orbital diagrams, and highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) electron transfer indicated intramolecular charge transfer (ICT). Theoretical studies confirmed the experimental HOMO energy trend and demonstrated its crucial importance in understanding each heterocycle's donor ability. Stokes shifts of up to ∼178 nm were observed, whereas absorptions and emissions were shifted deeper into the NIR region, resulting from ICT. Results suggest that this isoindigo fluorophore series has potential as a molecular scaffold for the development of efficient FI agents. The studied fluorophores can be further tuned with different donor fragments to enhance the ICT and facilitate in shifting the optical properties further into the NIR region.

Donor-acceptor (DÀ A) polymers have excellent electronic and optical properties that allow for their use in multiple areas of research, ranging from field-effect transistors to biosensing. However, traditional chemical polymerization strategies to form DÀ A polymers often require extensive purification and generate large amounts of waste. Electro-copolymerization of complex isoindigo-based copolymers is explored as a way to overcome traditional synthetic challenges. Herein, the electropolymerization and characterization of four isoindigo-based DÀ A copolymers are studied with: II-EDOT-T 3 , II-Thio-T 3 , II-Thio-T 3-TTDT 2 , and II-EDOT-T 3-TTDT 2. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis are used to confirm the composition of the polymers. Electrochemical impedance measurements show electron-transport resistance (R e) values as low as 74.7 Ω at selected potentials, indicating that highly conductive copolymers are present. These p-doped polymers exhibit absorption bands within the near-infrared region (NIR) with optical band gaps as low as 0.790 eV. Results confirm the electro-synthesized DÀ A copolymers exhibit excellent optical properties in the solid state and enhanced conductivity relative to conventional polymers; thus, affording materials with uses in a broad spectrum of applications.

As fluorescence bioimaging has increased in popularity, there have been numerous reports on designing organic fluorophores with desirable properties amenable to perform this task, specifically fluorophores with emission in the near-infrared II (NIR-II) region. One such strategy is to utilize the donor−π−acceptor−π−donor approach (D−π−A−π−D), as this allows for control of the photophysical properties of the resulting fluorophores through modulation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels. Herein, we illustrate the properties of thienothiadiazole (TTD) as an effective acceptor moiety in the design of NIR emissive fluorophores. TTD is a well-known electrondeficient species, but its use as an acceptor in D−π−A−π−D systems has not been extensively studied. We employed TTD as an acceptor unit in a series of two fluorophores and characterized the photophysical properties through experimental and computational studies. Both fluorophores exhibited emission maxima in the NIR-I that extends into the NIR-II. We also utilized electron paramagnetic resonance (EPR) spectroscopy to rationalize differences in the measured quantum yield values and demonstrated, to our knowledge, the first experimental evidence of radical species on a TTD-based small-molecule fluorophore. Encapsulation of the fluorophores using a surfactant formed polymeric nanoparticles, which were studied by photophysical and morphological techniques. The results of this work illustrate the potential of TTD as an acceptor in the design of NIR-II emissive fluorophores for fluorescence bioimaging applications.