Π-conjugated Small Molecules Research Articles

Molecular engineering strategy and optoelectronic properties of diaminobenzene-thiazole π-conjugated small donor molecules for high-performance organic solar cells

In this current study, the π-conjugated oligomers based on Thiazole units have been designed to understand the interaction of molecular orbitals and the influence of the substituents on the energetic HOMO-LUMO gap to build highly π-conjugated nanostructures. Their strong π-conjugated insight was also evidenced in gas phase through the photovoltaic properties using B3LYP/6-31G(d,p) level of theory for potential applications in organic electronic devices. Our research indicates geometries optimized structures, FMOs and chemical parameters were determined to predict optical properties of all oligomers. The results demonstrate that thiazole unit’s addition improved absorption above 400 nm at first excited states. The open-cicruit voltage Voc have been decreased from 2.22 V to 1.26 V in M1-a to M1-d. Whereas, LHE values was increased from 0.404 to 0.986 in M2-a to M2-d. All designed molecules have shown the enhanced optoelectronic characteristic that is plausible reason for their potential photoactive use in Organic Photovoltaics (OPVs) devices efficiencies.

On the importance of varying device thickness and temperature on the outcome of space-charge-limited current measurements

Space-charge-limited current (SCLC) measurements are commonly employed to characterize charge-transport properties of semiconductors used in next-generation thin-film optoelectronics, such as organic π-conjugated small molecules and polymers, and metal-halide perovskites. Despite the wide-spread adoption of the method, there is no community-wide consensus around how SCLC measurements should be performed, nor how the data should be analyzed and reported. While it is common to report device characteristics by employing a simplistic analytical model for fitting a single J-V curve obtained from a solitary device at room temperature—sometimes in a very select voltage range—expectedly, such an approach will often not give an accurate picture of the underlying physics. On that account, we here aim to highlight the importance of reporting values extracted from not just a solitary single-carrier device measured at room temperature, but from devices with different thicknesses measured at varying device temperature. We also highlight how the choice of device thickness is especially critical in determining what device and material characteristics can be extracted from SCLC measurements, and how this choice can greatly affect the conclusions drawn about the probed semiconducting material. While other factors could affect the outcome of an SCLC measurement and the subsequent analysis, we hope that the topics covered in this article will result in overall improved charge-transport characterization of thin-film semiconductors and initiate a broader discussion into SCLC metrology at large.

P-type π-conjugated BTPDS-8 organic molecule for broadband hybrid photodetector with organic/inorganic heterostructure

A novel p-type π-conjugated organic small molecule 3,7-bis(4-([2,2′:6′,2''-terpyridin]−4′-yl)phenyl)− 5H-dibenzo[a,d][7]annulen-5-one (named as BTPDS-8) in which terpyridinyl units are linked to the dibenzosuberenone backbone by a phenyl bridge was successfully synthesized in four reaction steps. The synthesized organic material BTPDS-8 was fully characterized using 1H NMR, 13C NMR, IR, and HRMS spectroscopy techniques. Then, eleven BTPDS-8/Si heterojunctions were fabricated having non-linear current-voltage characteristics. Among these devices, the one with the highest rectification ratio (with 8.43 ×105) was analyzed in detail under UV and IR light as well as different intensities of visible light. Experimental results showed that the device has good photoresponse performance under any light source in addition to self-driven mode characteristics. It was observed that the saturation current and barrier height increased, and the ideality factor decreased, depending on the light intensity under visible light. Photocurrent, on/off ratio, responsivity, detectivity and NPDR were calculated from the optical measurements. The broad spectrum photoresponse of the BTPDS-8/Si heterojunction from UV to IR demonstrated that the device has the potential to be used as a broadband photodetector. The best performance was obtained under 850 nm IR light. The detectivity values under IR light were 1.22 × 1010 Jones and 7.53 × 109 Jones for V= 0.0 volts (self-driven mode) and V= −2.0 volts, respectively.

Molecular Engineering for Enhanced Thermoelectric Performance of Single-Walled Carbon Nanotubes/π-Conjugated Organic Small Molecule Hybrids.

Hybridizing single-walled carbon nanotubes (SWCNTs) with π-conjugated organic small molecules (π-OSMs) offers a promising approach for producing high-performance thermoelectric (TE) materials through the facile optimization of the molecular geometry and energy levels of π-OSMs. Designing a twisted molecular structure for the π-OSM with the highest occupied molecular orbital energy level comparable to the valence band of SWCNTs enables effective energy filtering between the two materials. The SWCNTs/twisted π-OSM hybrid exhibits a high Seebeck coefficient of 110.4 ± 2.6 µV K-1 , leading to a significantly improved power factor of 2,136 µW m-1 K-2 , which is 2.6 times higher than that of SWCNTs. Moreover, a maximum figure of merit over 0.13 at room temperature is achieved via the efficient TE transport of the SWCNTs/twisted π-OSM hybrid. The study highlights the promising potential of optimizing molecular engineering of π-OSMs for hybridization with SWCNTs to create next-generation, efficient TE materials.

Thiadiazole based π-conjugated small molecule as donor material for highly stable and efficient bulk heterojunction organic solar cells

Thiadiazole based π-conjugated small molecule as donor material for highly stable and efficient bulk heterojunction organic solar cells

De novo design of highly efficient type-I photosensitizer based on π-conjugated oligomer for photodynamic eradication of multidrug-resistant bacterial infections

Traditional photosensitizers show limited singlet oxygen generation in hypoxic infection lesions, which greatly suppress their performance in antibacterial therapy. Meanwhile, there still is lack of feasible design strategy for developing hypoxia-overcoming photosensitizers agents. Herein, radical generation of π-conjugated small molecules is efficiently manipulated by an individual selenium (Se) substituent. With this strategy, the first proof-of-concept study of a Se-anchored oligo (thienyl ethynylene) (OT-Se) with high-performance superoxide radical (O2•−) and hydroxyl radical (•OH) generation capability is present, and achieves efficient antibacterial activities towards the clinically extracted multidrug-resistant bacteria methicillin-resistant S. aureus (MRSA) and carbapenem-resistant E. coli (CREC) at sub-micromolar concentration under a low white light irradiation (30 mW/cm2). The water-dispersible OT-Se shows a good bacteria-anchoring capability, biocompatibility, and complete elimination of multidrug-resistant bacteria wound infection in vivo. This work offers a strategy to boost type-I photodynamic therapy (PDT) performance for efficient antibacterial treatments, advancing the development of antibacterial agents.

Amplification of Dissymmetry for Circularly Polarized Photodetection by Cooperative Supramolecular Polymerization.

Circularly polarized photodetectors require chiral light absorption materials with high sensing efficiency and low costs. Here readily accessible point chirality has been introduced to dicyanostilbenes as the chiral source, facilitating remote chirality transfer to the π-aromatic core by cooperative supramolecular polymerization. The single-handed supramolecular polymers display powerful circularly polarized photodetection capability with a dissymmetry factor value as high as 0.83, superior to those of π-conjugated small molecules and oligomers. Strong chiral amplification occurs between the enantiopure sergeants and the achiral soldiers. The resulting supramolecular copolymers exhibit comparable photodetection efficiency to those of the homopolymeric ones, with a 90 % decrease in the enantiopure compound consumption. Therefore, cooperative supramolecular polymerization provides an effective yet economical avenue toward circularly polarized photodetection applications.

Functionalized Benzothiadiazole Non-Fused A-D-A'-D-A Small Molecules for Effective Electron Mobilities and Metal-free Photocatalysis.

Three non-fused A-D-A'-D-A π-conjugated metal-free small molecules BT-IT1, BT-IBT2 and BT2F-IBT3 have been synthesized and their absorption characteristics and redox properties, as well as charge carrier mobilities have been investigated. The resultant molecules exhibited broad absorption in the range of 325-600 nm in solutions and in thin films the absorption range is 350-700 nm. These new conjugated small molecules showed low-lying HOMO energy levels (-5.49 to -5.50 eV), deep LUMO energy levels (-3.67 to -3.69 eV) and narrow bandgaps of (Eg CV ) ∼0.79 eV. Appreciable electron mobilities for compounds BT-IBT2 and BT2F-IBT3 were 4.56×10-3 and 1.12×10-3 cm2 V-1 s-1 , respectively, obtained by space-charge limited current (SCLC) measurements. Additionally, excellent photocatalytic performances of BT-2T (6), BT2F-2T (10), BT-IT1, BT-IBT2 and BT2F-IBT3 for highly selective oxidation of thioanisole to desired sulfoxides under visible light irradiation were observed.

High Electrochromic Performance of Perylene Bisimide/ZnO Hybrid Films: An Efficient, Energy-Saving, and Green Route.

The composite or hybrid of organic and inorganic materials is one of the common ways to improve the properties of photoelectric functional materials. Perylene bisimide (PBI) derivatives, as large π-conjugated organic small molecules, are a class of photoelectric functional materials with excellent performance. However, there were few reports on PBIs in the electrochromic field due to the difficulty of film-forming caused by their generally poor solubility. Here, water-soluble PBI derivatives (PDI-COOH and PCl-COOH) were synthesized. The hybrid films (ZnO@PDI-COOH/PCl-COOH) formed by the coordination bond and π-π stacking were prepared via a simple solution immersion method. Fourier transform infrared spectrometry and X-ray diffraction as well as scanning electron microscopy, and energy-dispersive spectrometry results further confirmed the formation of hybrid films. At the same time, electrochemical and spectroelectrochemical analyses revealed that the films have reversible redox activity and cathodic electrochromic properties, which can change from orange-red to purple. The ZnO@PDI-COOH hybrid film formed by coordination bonds exhibits fast switching times (1.7 s colored time and 2.6 s bleached time), good stability (retain 92.41% contrast after 2400 cycles), a low driving voltage (-0.6-0 V), and a high coloration efficiency (276.14 cm2/C). The corresponding electrochromic devices also have good electrochromic properties. On this basis, a large-area (100 mm × 100 mm) electrochromic display device with fine patterning was fabricated by using the hybrid film, and the device shows excellent reversible electrochromic performance. This idea of constructing organic-inorganic hybrid materials with coordination bonds provides an effective, energy-saving, and green method, which is expected to promote the large-scale and fine production of electrochromic materials.

Effect of donor groups on the photovoltaic performance of benzothiadiazole-core substituted small molecules for fullerene-based bulk heterojunction organic solar cells

Herein, two symmetric donor-π-acceptor-π-donor-type π-conjugated small molecule donors (BTM and BTP), based on a benzothiadiazole central acceptor core unit and end-capped with electron-donating triphenylamine and 3,5-dimethoxyphenyl)vinyl, are synthesized via a multistep coupling reaction. The structural, thermal, optical, and electrochemical properties of the small molecules are systematically analyzed; subsequently, the molecules are applied as electron donor materials for bulk heterojunction organic solar cell fabrication. Compared with BTM, BTP exhibits a strong absorption spectrum with a precisely tuned optical bandgap (approximately 1.87 eV), desired morphology, and improved interfacial properties. The solar devices fabricated with BTP:PC71BM (1:2.5, w/w) exhibit a higher power conversion efficiency (PCE) of approximately 7.08% with an enhanced current density (JSC) of approximately 12.90 mA/cm2, high open-circuit voltage (VOC) of approximately 0.989 V, and fill factor (FF) of approximately 55.5% compared with BTM-based devices (approximately 4.86%). Notably, the high VOC achieved for the BTP:PC71BM (1:2.5, w/w) devices is a result of the deep-lying HOMO energy level and low LUMO energy offset (approximately 0.51 eV) between the BTP donor and PC71BM acceptor. The high hydrophobicity and stable surface morphology of BTP:PC71BM (1:2.5, w/w) exhibits a high room temperature stability approximately > 94% and retain 6.70% of PCE of its original PCE (7.08%) after 288 hr.

Solution-Processed Isoindigo- and Thienoisoindigo-Based Donor-Acceptor-Donor π-Conjugated Small Molecules: Synthesis, Morphology, Molecular Packing, and Field-Effect Transistor Characterization.

Molecular design and precise control of thin-film morphology and crystallinity of solution-processed small molecules are important for enhancing charge transport mobility of organic field-effect transistors and gaining more insight into the structure-property relationship. Here, two donor-acceptor-donor (D-A-D) architecture small molecules TRA-IID-TRA and TRA-TIID-TRA comprising an electron-donating triarylamine (TRA) and two different electron-withdrawing cores, isoindigo (IID) and thienoisoindigo (TIID), respectively, were synthesized and characterized. Replacing the phenylene rings of central IID A with thiophene gives a TIID core, which reduces the optical band gap and upshifts the energy levels of frontier molecular orbitals. The single-crystal structures and grazing-incidence wide-angle X-ray scattering (GIWAXS) analysis revealed that TRA-TIID-TRA exhibits the relatively tighter π-π stacking packing with preferential edge-on orientation, larger coherence length, and higher crystallinity due to the noncovalent S···O/S···π intermolecular interactions. The distinctly oriented and connected ribbon-like TRA-TIID-TRA crystalline film by the solution-shearing process achieved a superior hole mobility of 0.89 cm2 V-1 s-1 in the organic field-effect transistor (OFET) device, which is at least five times higher than that (0.17 cm2 V-1 s-1) of TRA-IID-TRA with clear cracks. Eventually, rational modulation of fused core in the π-conjugated D-A-D small molecule provides a new understanding of structural design for enhancing the performance of solution-processed organic semiconductors.

Dynamic Excitons in Nitrile-Functionalized Ladder-Type Oligo(p-Phenylene)s By Pulse Radiolysis Coupled with Time-Resolved Infrared Spectroscopy

Research and development efforts toward organic solar cells (OSCs) for large-scale power generation have continued unabated throughout the world. In recent years, OSCs based on π-conjugated polymers and small molecules have received increasing interest due to favorable electronic properties, component versatility, and low production and installation costs. Despite the progress, many improvements are still needed prior to widespread commercialization, involving device efficiency, lifetime, and cost. Of these, increasing device efficiency, particularly power conversion efficiency (PCE), is the most challenging task. The currently achievable PCE, for example, is only 17.3%.1 The key to achieving high PCE is the search for new organic conjugated molecules that are capable of harvesting light, and transferring and transporting charges promptly and efficiently. This requires a full understanding of how electrons and holes are localized and delocalized in organic conjugated molecules.Using time-resolved infrared (TRIR) detection combined with pulse radiolysis, Mani and co-workers2 have measured experimentally the degree of localization of an excess electron in a series of nitrile-functionalized oligofluorenes by the spectral shifts of nitrile vibrations. The nitrile vibrational bands in anions respond sensitively to the degree of electron delocalization (IR shifts) and the structural changes (IR linewidth). The electron is found to move back and forth within the oligomers, likely controlled by the movement of dihedral angles between monomer units.Unlike the non-coplanarity of the fluorenyl-fluorenyl backbone in oligofluorenes, the rigid and planar structure of ladder-type, oligo(p-phenylene)s (Scheme 1)3 would facilitate π-electron delocalization and thus improve the multiphoton absorption response. Such a structure would also increase photoluminescence efficiency with enhanced thermal and photochemical stability. To investigate the coupling between charge distribution and vibrational motion and vibronic coupling, we incorporate nitrile group in each compound as the infrared reporter group.In this talk, we report our molecular syntheses and characterizations of two of the title compounds (L3PCN and L4PCN, both neutral compounds and their radical anions) by TRIR followed by pulse radiolysis. Having no flexible dihedral angles, L3PCN and L4PCN exhibit sharper IR bands of the nitrile vibration than the oligofluorenes with the same number of benzene rings and some dihedral angles. Our results further demonstrate that the linewidth of the nitrile vibration, together with the IR shifts and intensities, reports on structural and accompanying electronic fluctuations,2 that is, on the dynamic excitons. References (1) Meng, L. X.; et al. Science 2018, 361, 1094.(2) Mani, T.; et al. Journal of the American Chemical Society 2015, 137, 10979.(3) Scherf, U.; et al. Makromolekulare Chemie-Rapid Communications 1991, 12, 489. Figure 1

Highly Efficient Perovskite Solar Cell Based on PVK Hole Transport Layer.

A π-conjugated small molecule N, N’-bis(naphthalen-1-yl)-N, N’-bis(phenyl)benzidine (NPB) was introduced into poly(9-vinylcarbazole) (PVK) as a hole transport layer (HTL) in inverted perovskite solar cells (PSCs). The NPB doping induces a better perovskite crystal growth, resulting in perovskite with a larger grain size and less defect density. Thus, the VOC, JSC, and FF of the PSC were all enhanced. Experimental results show that it can be ascribed to the reduction of surface roughness and improved hydrophilicity of the HTL. The effect of NPB on the aggregation of PVK was also discussed. This work demonstrates the great potential of PVK as the HTL of PSCs and provides an attractive alternative for HTL to realize high-efficiency PSCs.

Stable and Solution-Processable Cumulenic sp-Carbon Wires: A New Paradigm for Organic Electronics.

Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp2 -hybridized carbon molecules, either in the form of π-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to molecular devices. The recent observation of the field-effect in microcrystalline cumulenes suggests their potential applications in solution-processed thin-film transistors but concerns surrounding the stability and electronic performance have precluded developments in this direction. In the present study, ideal field-effect characteristics are demonstrated for solution-processed thin films of tetraphenyl[3]cumulene, the shortest semiconducting CAW. Films are deposited through a scalable, large-area, meniscus-coating technique, providing transistors with hole mobilities in excess of 0.1cm2 V-1 s-1 , as well as promising operational stability under dark conditions. These results offer a solid foundation for the exploitation of a vast class of molecular semiconductors for organic electronics based on sp-hybridized carbon systems and create a previously unexplored paradigm.

Vapor-solid interfacial reaction and polymerization for wafer-scale uniform and ultrathin two-dimensional organic films

Chemical vapor deposition is a conventional synthesis method for growing large-scale and high-quality two-dimensional materials, such as graphene, hexagonal boron nitride, and transition-metal dichalcogenides. For organic films, solution-based methods, such as inkjet printing, spin coating, and drop and micro-contact printing, are commonly used. Herein, we demonstrate a general method for growing wafer-scale continuous, uniform, and ultrathin (2–5 nm) organic films. This method is based on a copper (Cu) surface-mediated reaction and polymerization of several equivalent bromine (Br)-containing π-conjugated small molecules (C12S3Br6, C24H4O2Br2, and C24H12Br2N4), in which local surface-mediated polymerization and internal π-π interactions among organic molecules are responsible for the dimension and uniformity control of the thin films. Specifically, the growth rate and morphology of thin films were found to be Cu-facet-dependent, and single-crystal Cu(111) surfaces could improve the uniformity of thin films. In addition, the number of Br groups and size of organic molecules were critical for crystallinity and thin-film formation. This method can be used to fabricate heterostructures, such as organic film/graphene, giving room for various functional materials and device applications.

Hydrophobic π-conjugated organic small molecule as a multi-functional interface material enables efficient and stable perovskite solar cells

Surface treatment of perovskite films with interface materials is an effective strategy to resolve trap-mediated nonradiative recombination toward high efficiency and stability of perovskite solar cells (PSCs). However, interface materials for multi-functional treatment have been rarely investigated in PSCs. In this work, a novel pyrene-based organic material (TAAPyr) is first introduced as a defect passivation layer and a protect layer against moisture for PSCs application. With the TAAPyr interfacial modification, both perovskite surface defects and nonradiative recombination are effectively decreased as well as the carrier transport in device is also enhanced, As a consequence, the best power conversion efficiencies (PCE) up to 22.45% for TAAPyr-based device was obtained, clearly outperforming the control one (20.37%). Moreover, it was found that the π-conjugated TAAPyr can promote intermolecular face-to-face stacking on the surface perovskite film, which is favorable to making the perovskite surface more hydrophobic and consequently enhance PSCs long-term stability. The un-encapsulated PSCs can retain 92% of the initial PCE after storage for 600 h at ∼65% RH, in comparison with 64% efficiency retention of the device without TAAPyr under the same conditions. This work presents a new strategy to enhance the efficiency and stability of PSCs by multi-functional π–conjugated passivator.

Controlled Assembly of Conjugated Ladder Molecules with Different Bridging Structures toward Optoelectronic Application.

Structural design of organic π-conjugated small molecules allows the energy band structure and electronic properties of the molecules to be tuned as needed, which provides a feasible strategy for enhancing the performance of optoelectronic devices. The introduction of bridging structures is a common structural modification method to adjust the rigidity and coplanarity of the molecular backbone, thus affecting the molecular packing. However, patterning of organic single-crystalline microstructures based on conjugated ladder molecules with different bridging structures still remains challenging for large-area integration of optoelectronic devices. In this paper, a controlled dewetting process is applied to obtain organic single-crystalline arrays with precise positioning and a regular morphology based on two isomers with silicon-oxygen bridging and their two carbon-oxygen-bridged analogues. Molecules with different bridging structures show disparate packing models due to the difference of dihedral angles and ring tensions. A microwire-array ultraviolet photodetector based on the oxygen-silicon-bridging ladder molecule exhibits a high light on/off ratio of 24 and a responsivity of 0.63 mA W-1 owing to the effective π-π stacking governed by the molecular planarity. This work not only provides a universal method for the integration of organic optoelectronic devices but also explains the effect of bridging structure engineering on molecular assembly and optoelectronic performance.

Inside Back Cover: Volume 2 Issue 3

Inside back cover image: Crystal structure of π-conjugated small molecules and polymers is fundamentally critical to understand the multilevel microstructures. However, determining the crystal structure of conjugated polymers remains a significant challenge. Jian Pei and coworkers build the possible crystal structures of eight typical conjugated polymers, covering several widely used molecular segments in organic optoelectronics. These crystal structures are modeled by combining synchrotron X-ray diffractions and molecular simulations, which compose a crystal structure database of conjugated polymers, providing a new platform to predict the possible packing structures and charge transport properties of related polymers. Such crystal structure database of conjugated polymers aims to accelerate the intelligent design of high-performance conjugated polymers. (DOI: https://doi.org/10.1002/smm2.1053)

Pyrene-cyanostyrene-pyridine triad: Multi-stimuli responsive fluorescent emitter and mitochondrial imaging

Tuning the fluorescence of π-conjugated small organic molecules through the structural modifications and in the presence of external stimuli have found immense applications ranging from sensing, switching, optoelectronics to bioimaging. Herein, we demonstrated a simple design strategy for the synthesis of a pyrene-cyanostyrene-pyridine molecular triad (PYBNP) using a cost-effective, one-step Knoevenagel condensation between 1-pyrenecarboxaldehyde and 2-(4-(pyridin-4-yl)phenyl)acetonitrile. PYBNP exhibited strong solid-state emission having a quantum yield of ∼ 36 ± 3% due to the deactivation of nonradiative decay channels through the restriction of intramolecular rotations and reduced π-π stacking interactions as revealed from the crystal structure analysis. Similarly, PYBNP was found to be highly emissive in the constrained environments like viscous medium and aggregated state. The optical properties of PYBNP could be tuned by the UV light-mediated dynamic Z/E-isomerization as elucidated through fluorescence spectroscopy and NMR analysis. Additionally, the pyridinic nitrogen centre allowed the fabrication of methylated analog (PYBNPM; a new cationic photoresponsive species). The cationic PYBNPM showed a better solvatochromic behavior contrary to PYBNP due to the efficient intramolecular charge transfer (ICT). The different crystal packing of PYBNP and that of hexafluorophosphate salts of PYBNPM led to distinct fluorescent properties in the solid-state. As a preliminary exploration, the cationic PYBNPM(PF6) was employed for the specific imaging of the mitochondria through multiple fluorescence channels in an aqueous medium. The cost-effective and viable design strategy demonstrated for the fabrication of a simple molecular triad holds the promise for the emergence of new functional fluorescent molecules to molecular materials for task-specific applications.

Efficient Colorimetric Fluoride Anion Sensor Based on π-Conjugated Carbazole Small Molecule.

The ability to detect fluoride anions with high selectivity and sensitivity by using the naked eye is crucial yet challenging. In this study, a novel, simple conjugated organic dye, N-tert-butyldimethylsilyl-3,6-diiodocarbazole (CA-TBMDS) was developed and used for the first time as a colorimetric sensor for fluoride. CA-TBMDS was found to be a highly sensitive fluoride chemosensor, with a detection limit as low as 3 × 10−5 M. The reaction of CA-TBMDS with fluoride anions in a tetrahydrofuran solution resulted in a color change from colorless to yellow under ambient light, which can be discriminated by the naked eye. The sensor operated via intermolecular proton transfer between the amide units and the fluoride anion, as confirmed by proton nuclear magnetic resonance titration. CA-TBMDS is not only highly sensitive to fluoride anions, but also exhibits high sensitivity in the presence of various ions. This work demonstrates that N-butyldimethylchlorosilane-based organic dyes have prospective utility as a type of fluoride anion chemosensor.