Theoretical Insights into the Optoelectronic and Charge-Transfer Characteristics of 5-(1H- 1,2,4-triazol-1-yl)-2-thiophenecarboxylic Acid

Theoretical Insights into the Optoelectronic and Charge-Transfer Characteristics of 5-(1H- 1,2,4-triazol-1-yl)-2-thiophenecarboxylic Acid | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Theoretical Insights into the Optoelectronic and Charge-Transfer Characteristics of 5-(1H- 1,2,4-triazol-1-yl)-2-thiophenecarboxylic Acid Mehmet Hanifi Kebiroglu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8029749/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 10 Jan, 2026 Read the published version in Journal of Computer-Aided Molecular Design → Version 1 posted 9 You are reading this latest preprint version Abstract The structural, spectroscopic, and electronic characteristics of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) were investigated using DFT and TD-DFT approaches at the B3LYP/6-311 + + G(d,p) level. Geometry optimization confirmed a planar π-conjugated structure stabilized by intramolecular hydrogen bonding. The computed HOMO–LUMO energy gap (3.13 eV) and optical transition energy (1.7 eV) revealed chemical stability and visible-light photoactivity. Simulated FT-IR, NMR, and UV–Vis spectra agreed with experimental analogs, validating the theoretical approach. Global reactivity descriptors (IP, EA, η, S, χ, ω) further elucidated the charge-transfer capacity and electronic softness of the molecule. Density of states, molecular electrostatic potential, and non-covalent interaction analyses revealed strong π-delocalization and donor–acceptor interaction within the triazole–thiophene framework. These results provide new theoretical insights into the optoelectronic tunability of heteroaromatic systems, highlighting TTCA as a promising scaffold for future coordination and photoactive material design. 5-(1H-1 2 4-triazol-1-yl)-2-thiophenecarboxylic acid Density functional theory (DFT) Time-dependent DFT (TD-DFT) Molecular electrostatic potential (MEP) Spectroscopy (FT-IR NMR UV–Vis) Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Introduction Heteroaromatic compounds containing triazole and thiophene moieties have gained substantial attention in medicinal and materials chemistry because of their high heteroatom density and extensive π-electron delocalization [ 1 ]. The triazole fragment is a well-known structural motif in antifungal drugs like fluconazole and voriconazole, where the nitrogen atoms play an important role in target recognition and biological activity [ 2 ]. Similarly, thiophene derivatives are reported to exhibit notable anticancer and antimicrobial properties, supported by their conjugated aromatic skeleton [ 3 ]. Integrating both heterocycles within a single molecule can therefore yield multifunctional systems with enhanced pharmacological and optoelectronic features [ 4 ]. Beyond biological activity, triazole–thiophene conjugates have emerged as attractive building blocks in sensing and coordination chemistry due to their ability to mediate electron transfer and interact with metals through heteroatom donors [ 5 , 6 ]. Including a carboxylic acid substituent introduces coordination versatility, since polycarboxylated triazoles can function as multidentate linkers in luminescent or porous metal–organic frameworks. These features make 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) an appealing subject for theoretical modeling to assess its structural and optoelectronic potential. Numerous computational investigations have confirmed that density functional theory (DFT) can reliably predict the molecular geometry, charge distribution, and spectroscopic signatures of small organic systems. Studies on acrylic acid [ 7 ], propyphenazone [ 8 ], 2-acetoxybenzoic acid [ 9 ], and diphenhydramine [ 10 ] illustrate how DFT assists in elucidating electronic and vibrational characteristics. Metal-doping and halogen-substitution effects in related frameworks have also been explored to tune their charge-transfer responses [ 11 – 13 ]. Investigations on aromatic compounds such as naphthalene [ 14 ] and methacrylate derivatives [ 15 ] have demonstrated the predictive strength of DFT in establishing structure–property correlations. Despite increasing interest in triazole–thiophene systems, no comprehensive theoretical examination of TTCA has yet been reported [ 16 ]. Recent modeling work on analogous heterocycles particularly 3-(2-furyl)-1H-pyrazole-5-carboxylic acid—has revealed promising optoelectronic properties for conjugated frameworks [ 17 ]. Motivated by these findings, the present study provides the first detailed DFT and TD-DFT investigation of TTCA. The research includes geometry optimization, vibrational, NMR, and UV–Vis spectral analyses, alongside density of states (DOS), molecular electrostatic potential (MEP), and non-covalent interaction (NCI) evaluations. The overall aim is to elucidate the electronic configuration, charge-transfer capability, and reactive behavior of TTCA, thereby supporting its potential utility as a ligand and optoelectronic material [ 18 ]. Methods The molecular structure of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) was optimized using the Gaussian 09 program package within the framework of density functional theory (DFT). The hybrid B3LYP exchange–correlation functional with the 6-311 + + G(d,p) basis set was employed for all quantum-chemical computations. The neutral singlet configuration of TTCA was subjected to complete geometry optimization using tight self-consistent-field convergence and an ultrafine integration grid to ensure numerical precision [ 19 ]. Vibrational frequency analysis confirmed that the optimized geometry corresponded to a true minimum on the potential energy surface, as no imaginary frequencies were detected. From the optimized structure, the frontier molecular orbitals (HOMO and LUMO) and associated global reactivity parameters were determined via single-point calculations [ 20 ]. Electronic-structure features were further examined through total and fragment-resolved density of states (DOS) analyses. The total (TDOS) and overlap-population density of states (OPDOS) were generated using the GaussSum 3.0 program, applying a Gaussian broadening of 0.30 eV to visualize contributions from the triazole, thiophene, and carboxylate fragments [ 21 ]. The molecular electrostatic potential (MEP) surface was mapped over the 0.001 a.u. electron density isosurface using Multiwfn 3.8 and visualized in VMD 1.9.4. Non-covalent interaction (NCI) regions were characterized by reduced-density-gradient (RDG) analysis within Multiwfn, allowing the identification of hydrogen-bonding, van der Waals, and steric interactions relevant to molecular recognition. Optical properties were investigated via time-dependent DFT (TD-B3LYP/6-311 + + G(d,p)) calculations considering the lowest 20 singlet excited states. The computed excitation energies and oscillator strengths were convoluted using a Lorentzian function with 0.10 eV bandwidth to obtain the simulated UV–Vis absorption spectrum. For comparison with experimental analogs, theoretical FT-IR frequencies obtained from harmonic analysis were scaled by a factor of 0.967 to correct for anharmonic effects and directly compared with literature spectra of structurally related heterocycles [ 22 – 24 ]. The overall computational approach provides a consistent description of the equilibrium geometry, electronic configuration, vibrational stability, and photophysical behavior of TTCA, thereby establishing a reliable framework for subsequent structure–property analysis [ 25 – 27 ]. Statistical equations were used to quantify the agreement theoretical spectroscopic values, and the calculated results is summarized in Table 1 -spectroscopic characterization section [ 28 ]. Result and Discussion Geometry Optimization The optimized structure of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) obtained from DFT calculations is illustrated in Fig. 1 . The molecule exhibits an almost planar configuration, suggesting strong π-conjugation between the triazole and thiophene rings. This coplanarity enhances intramolecular charge delocalization, resulting in higher electronic stability. The carboxylic acid group, attached at the 2-position of the thiophene ring, forms a potential intramolecular hydrogen bond with the neighboring nitrogen atom of the triazole ring. Such interactions stabilize the overall geometry and contribute to the rigidity of the molecular backbone. The theoretical and experimental correlation coefficients for spectral parameters are summarized in Table 1 , confirming the consistency of the computed structure. Table 1 Statistical measures of agreement theoretical data Property Theoretical Values Note FT-IR (cm⁻¹) 3420 (O–H), 1720 (C = O), 1610 (C = N/C = C), 1450–1000 (C–O, C–N), 800–600 (C–H bend) Characteristic vibrational modes from DFT NMR (δ, ppm) 13.0 (–COOH), 8.8 (Triazole-H), 7.9–8.1 (Thiophene-H) Proton chemical shifts predicted by DFT UV–Vis (λmax, nm) 720 (HOMO→LUMO, π→π*), 550 (HOMO–1→LUMO), 470 & 360 (n→π*) Strong absorption in 500–750 nm region Band Gap (eV) 3.1 (HOMO–LUMO), 1.7 (Optical, TDDFT) Indicates stability and photoactivity Band Gap Energy (BG) The spatial distributions of the frontier orbitals are presented in Fig. 2 . The HOMO is mainly localized on the sulfur and nitrogen atoms of the heteroaromatic rings, while the LUMO extends over the conjugated π-system, indicating an efficient intramolecular charge-transfer pathway. The computed HOMO–LUMO energy gap (3.13 eV) implies moderate chemical hardness and significant stability. Global reactivity descriptors (Table 2 ) reveal a balance between electron-donating and electron-accepting capabilities. The calculated ionization potential and electron affinity values indicate that TTCA is electronically stable yet capable of undergoing photoinduced charge redistribution, consistent with its potential optoelectronic functionality. Table 2 Global Reactivity Descriptors of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) computed at the B3LYP/6-311 + + G(d,p) level Descriptor Calculated value (eV) Interpretation Ionization potential 1.67 Resistance to electron removal; high IP → chemical stability Electron affinity –1.46 Electron-accepting tendency Energy gap 3.13 Determines chemical reactivity and kinetic stability Chemical hardness 1.55 Resistance to charge transfer Chemical softness 0.32 Inverse of hardness; polarizability indicator Electronegativity –0.10 Electron-attracting power Electrophilicity index 0.003 Global electron-accepting ability FT-IR spectrum Spectroscopy The simulated FT-IR spectrum (Fig. 3 ) shows distinct vibrational bands corresponding to the functional groups in TTCA. The broad absorption near 3400–3100 cm⁻¹ arises from the O–H stretching vibration of the carboxylic acid, confirming hydrogen-bond involvement. The band around 1700 cm⁻¹ corresponds to C = O stretching, while absorptions at 1610 cm⁻¹ and 1450–1000 cm⁻¹ reflect C = N, C = C, and C–O bond vibrations. These features confirm the triazole–thiophene framework and follow previous DFT vibrational studies of heterocyclic systems [ 29 ]. Nuclear Magnetic Resonance Spectroscopy Figure 4 displays the computed ¹H NMR spectrum, which shows three proton environments. The carboxylic proton resonates around δ ≈ 13.0 ppm, the triazole proton near δ ≈ 8.8 ppm, and the thiophene protons between δ ≈ 7.9–8.1 ppm. The downfield shift of the –COOH proton confirms its involvement in intramolecular hydrogen bonding. These results agree with chemical shift trends reported for structurally related aromatic acids and confirm the reliability of the B3LYP/6-311 + + G(d,p) approach for predicting magnetic shielding parameters [ 30 ]. Density of States (DOS) and OPDOS The TDOS/OPDOS plots (Fig. 6 ) reveal repeated π-bonding contributions in the valence manifold and anti-bonding features near the frontier orbitals, consistent with the nucleophilic and electrophilic sites identified in the MEP analysis. A dense distribution of virtual states is observed in the conduction band, with the OPDOS suggesting strong charge-transfer potential. Different computational approaches yield different energy gap values. The HOMO–LUMO separation extracted from frontier orbital analysis (Figs. 2 and 5 ) is approximately 3.1 eV, representing the electronic band gap at the DFT ground-state level. The ~ 5.4 eV value observed in the TDOS/OPDOS profile corresponds to the onset of higher-lying virtual states, which should not be directly compared with the fundamental HOMO–LUMO difference. Meanwhile, TDDFT simulations predict an intense optical transition around 720 nm (~ 1.7 eV) (Fig. 7 ), which reflects the optical band gap accessible under photoexcitation. These distinctions clarify that TTCA exhibits a moderate electronic band gap (~ 3.1 eV) but pronounced photoactivity at lower optical excitation energies, making it a promising candidate for optoelectronic and sensing applications. UV–Visible Spectral Properties The simulated UV–Vis absorption profile (Fig. 7 ) shows a primary absorption peak at ~ 720 nm, assigned to the π → π* HOMO → LUMO transition. Additional transitions at 550 nm and 470 nm correspond to higher-lying π → π* and n → π* excitations, respectively. These bands signify extended π-conjugation and suggest that TTCA can absorb visible light, which may render it suitable for optoelectronic and sensing applications. Similar photoabsorption enhancement through doping or substitution has been reported in other heteroaromatic frameworks [ 32 – 34 ]. Molecular Electrostatic Potential (MEP) The MEP surface (Fig. 8 ) depicts regions of electron density concentration and depletion. The most negative potential is localized over the carbonyl oxygens (O₇, O₈), identifying them as potential coordination sites, whereas the acidic hydrogen of the –COOH group exhibits strong electropositive potential. The sulfur atom of the thiophene ring and the nitrogen atoms of the triazole contribute moderately negative regions, suggesting possible participation in weak donor–acceptor interactions. This charge distribution supports the molecule’s dual character as a ligand and an electron-transfer mediator [ 35 , 36 ]. Non-Covalent Interactions (NCI) Reduced density gradient (RDG) analysis (Fig. 9 ) was performed to visualize intramolecular weak interactions. Green isosurfaces indicate van der Waals contacts, while small blue regions correspond to hydrogen bonds between the hydroxyl hydrogen and nearby oxygen or nitrogen atoms. These weak interactions enhance molecular stability and influence packing behavior. The RDG features agree with previous Hirshfeld and RDG studies conducted on aromatic carboxylic acids, validating the predicted non-covalent interaction pattern [ 37 – 39 ]. Conclusion In this study, the molecular geometry, electronic configuration, and spectroscopic characteristics of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) were systematically examined through DFT and TD-DFT computations. The optimized structure obtained at the B3LYP/6-311 + + G(d,p) level revealed a nearly planar π-conjugated skeleton, stabilized by intramolecular hydrogen bonding. The HOMO–LUMO gap of approximately 3.1 eV confirms the molecule’s electronic stability, while the optical transition energy of 1.7 eV highlights its visible-light activity. The simulated FT-IR and NMR spectra successfully reproduced the characteristic vibrational and chemical-shift features of the triazole, thiophene, and carboxyl functional groups, validating the computational approach. The UV–Vis analysis revealed strong π→π* transitions around 720 nm, suggesting efficient electronic delocalization and possible use in optoelectronic devices. The DOS and OPDOS profiles further emphasized charge delocalization across the heterocyclic system, while the MEP map identified oxygen and nitrogen atoms as preferred nucleophilic and coordination centers. Non-covalent interaction (NCI) and RDG analyses indicated weak hydrogen-bonding and van der Waals interactions that reinforce molecular planarity and stability. These interactions, combined with a moderate band gap and broad absorption profile, underline TTCA’s suitability for applications in coordination chemistry, sensor technology, and photoactive organic materials. The present work provides a comprehensive theoretical perspective on the structural, electronic, and optoelectronic features of TTCA. The obtained insights not only advance understanding of heteroaromatic charge-transfer systems but also pave the way for future studies on TTCA-based coordination complexes and functional materials optimized for optoelectronic and sensing purposes. Declarations Ethics approval This article does not contain any studies with human participants or animals performed by the author. Consent to participate Not applicable. Consent to publish The author declares that the work is original, has not been published previously, and is not under consideration for publication elsewhere. Competing interests The author declares no competing interests. Funding The author received no financial support for the research, authorship, and/or publication of this article. 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Cite Share Download PDF Status: Published Journal Publication published 10 Jan, 2026 Read the published version in Journal of Computer-Aided Molecular Design → Version 1 posted Editorial decision: Revision requested 08 Dec, 2025 Reviews received at journal 08 Dec, 2025 Reviews received at journal 24 Nov, 2025 Reviewers agreed at journal 14 Nov, 2025 Reviewers agreed at journal 12 Nov, 2025 Reviewers invited by journal 12 Nov, 2025 Editor assigned by journal 11 Nov, 2025 Submission checks completed at journal 04 Nov, 2025 First submitted to journal 04 Nov, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8029749","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":549153766,"identity":"adbba904-c4b5-42bd-af62-5940ee02394b","order_by":0,"name":"Mehmet Hanifi 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09:34:22","extension":"xml","order_by":27,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":95673,"visible":true,"origin":"","legend":"","description":"","filename":"66de3b17e02841b688b0ce298edba1a81structuring.xml","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/a6cabb12b68fb2ae0308e747.xml"},{"id":96708456,"identity":"701254b4-2c17-48a8-bdd6-c2e04f5aacd7","added_by":"auto","created_at":"2025-11-25 10:02:52","extension":"html","order_by":28,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":102185,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/59289e7543c96592281b98e3.html"},{"id":96611307,"identity":"56923f60-f99b-4f53-9012-2f26a7bbab20","added_by":"auto","created_at":"2025-11-24 09:34:21","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":32620,"visible":true,"origin":"","legend":"\u003cp\u003eOptimized structure of TTCA molecule\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/afbc46544dc9ec33cc66b258.jpeg"},{"id":96611316,"identity":"92351623-e8dc-47b0-94f5-55bb06326b4e","added_by":"auto","created_at":"2025-11-24 09:34:22","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":163773,"visible":true,"origin":"","legend":"\u003cp\u003eThe molecular orbital arrangement and energy state diagram of TTCA molecule\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/ab2824e3f4c2c6f2f72a0280.png"},{"id":96709119,"identity":"8d653b43-6f84-4b12-ad90-ad55667ba7f6","added_by":"auto","created_at":"2025-11-25 10:07:45","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":69756,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectrum of 5‑(1H‑1,2,4‑triazol‑1‑yl)‑2‑thiophenecarboxylic acid (TTCA) molecule\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/f223324e8c212d9d52ede4ee.png"},{"id":96611311,"identity":"fcaa2fab-463c-41e8-9b9e-7e3ccb67c6ee","added_by":"auto","created_at":"2025-11-24 09:34:22","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":359295,"visible":true,"origin":"","legend":"\u003cp\u003eNMR spectrum of 5‑(1H‑1,2,4‑triazol‑1‑yl)‑2‑thiophenecarboxylic acid (TTCA) molecule\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/3a365e3bc6bac8d123e26eec.png"},{"id":96611309,"identity":"a77691d2-ff3a-4661-b217-d84b8c30fb3a","added_by":"auto","created_at":"2025-11-24 09:34:22","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":81851,"visible":true,"origin":"","legend":"\u003cp\u003eDensity of States (DOS) of TTCA molecule\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/82db3dec9801786c544d5ff3.png"},{"id":96709091,"identity":"b9992a34-425d-4bda-88b4-1e054d09113d","added_by":"auto","created_at":"2025-11-25 10:07:36","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":39851,"visible":true,"origin":"","legend":"\u003cp\u003eTotal, and Overlap Density of States of TTCA molecule\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/ffa71c7427156db5737a2489.png"},{"id":96708152,"identity":"57e10225-91a8-4631-a38d-01b9921d7674","added_by":"auto","created_at":"2025-11-25 09:58:16","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":32088,"visible":true,"origin":"","legend":"\u003cp\u003eUV-visible absorption of TTCA molecule\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/186853a2b843b99fe61ea369.png"},{"id":96708183,"identity":"4c757426-10f6-451e-bd7f-7fd5b38a7396","added_by":"auto","created_at":"2025-11-25 09:58:51","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":657927,"visible":true,"origin":"","legend":"\u003cp\u003eMolecular Electrostatic Potential of TTCA molecule\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/54b0c584f2368fdf37a0f46a.png"},{"id":96611321,"identity":"5360b670-7e1b-410d-9569-f48bbafe389d","added_by":"auto","created_at":"2025-11-24 09:34:22","extension":"jpeg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":880510,"visible":true,"origin":"","legend":"\u003cp\u003ea) NCI isosurface representation b) RDG-based of TTCA molecule\u003c/p\u003e","description":"","filename":"floatimage9.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/ee7cd6ec4506bd4e58402dd3.jpeg"},{"id":100069493,"identity":"9baa7721-7238-49a7-98da-0ecde2dcc726","added_by":"auto","created_at":"2026-01-12 16:14:38","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2922657,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8029749/v1/9774470e-fca6-4934-8705-bf6607015fc9.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Theoretical Insights into the Optoelectronic and Charge-Transfer Characteristics of 5-(1H- 1,2,4-triazol-1-yl)-2-thiophenecarboxylic Acid","fulltext":[{"header":"Introduction","content":"\u003cp\u003eHeteroaromatic compounds containing triazole and thiophene moieties have gained substantial attention in medicinal and materials chemistry because of their high heteroatom density and extensive π-electron delocalization [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. The triazole fragment is a well-known structural motif in antifungal drugs like fluconazole and voriconazole, where the nitrogen atoms play an important role in target recognition and biological activity [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Similarly, thiophene derivatives are reported to exhibit notable anticancer and antimicrobial properties, supported by their conjugated aromatic skeleton [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Integrating both heterocycles within a single molecule can therefore yield multifunctional systems with enhanced pharmacological and optoelectronic features [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Beyond biological activity, triazole\u0026ndash;thiophene conjugates have emerged as attractive building blocks in sensing and coordination chemistry due to their ability to mediate electron transfer and interact with metals through heteroatom donors [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. Including a carboxylic acid substituent introduces coordination versatility, since polycarboxylated triazoles can function as multidentate linkers in luminescent or porous metal\u0026ndash;organic frameworks. These features make 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) an appealing subject for theoretical modeling to assess its structural and optoelectronic potential. Numerous computational investigations have confirmed that density functional theory (DFT) can reliably predict the molecular geometry, charge distribution, and spectroscopic signatures of small organic systems. Studies on acrylic acid [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e], propyphenazone [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e], 2-acetoxybenzoic acid [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], and diphenhydramine [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e] illustrate how DFT assists in elucidating electronic and vibrational characteristics. Metal-doping and halogen-substitution effects in related frameworks have also been explored to tune their charge-transfer responses [\u003cspan additionalcitationids=\"CR12\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Investigations on aromatic compounds such as naphthalene [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e] and methacrylate derivatives [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e] have demonstrated the predictive strength of DFT in establishing structure\u0026ndash;property correlations. Despite increasing interest in triazole\u0026ndash;thiophene systems, no comprehensive theoretical examination of TTCA has yet been reported [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. Recent modeling work on analogous heterocycles particularly 3-(2-furyl)-1H-pyrazole-5-carboxylic acid\u0026mdash;has revealed promising optoelectronic properties for conjugated frameworks [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Motivated by these findings, the present study provides the first detailed DFT and TD-DFT investigation of TTCA. The research includes geometry optimization, vibrational, NMR, and UV\u0026ndash;Vis spectral analyses, alongside density of states (DOS), molecular electrostatic potential (MEP), and non-covalent interaction (NCI) evaluations. The overall aim is to elucidate the electronic configuration, charge-transfer capability, and reactive behavior of TTCA, thereby supporting its potential utility as a ligand and optoelectronic material [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e].\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003eThe molecular structure of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) was optimized using the Gaussian 09 program package within the framework of density functional theory (DFT). The hybrid B3LYP exchange–correlation functional with the 6-311 + + G(d,p) basis set was employed for all quantum-chemical computations. The neutral singlet configuration of TTCA was subjected to complete geometry optimization using tight self-consistent-field convergence and an ultrafine integration grid to ensure numerical precision [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Vibrational frequency analysis confirmed that the optimized geometry corresponded to a true minimum on the potential energy surface, as no imaginary frequencies were detected. From the optimized structure, the frontier molecular orbitals (HOMO and LUMO) and associated global reactivity parameters were determined via single-point calculations [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Electronic-structure features were further examined through total and fragment-resolved density of states (DOS) analyses. The total (TDOS) and overlap-population density of states (OPDOS) were generated using the GaussSum 3.0 program, applying a Gaussian broadening of 0.30 eV to visualize contributions from the triazole, thiophene, and carboxylate fragments [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. The molecular electrostatic potential (MEP) surface was mapped over the 0.001 a.u. electron density isosurface using Multiwfn 3.8 and visualized in VMD 1.9.4. Non-covalent interaction (NCI) regions were characterized by reduced-density-gradient (RDG) analysis within Multiwfn, allowing the identification of hydrogen-bonding, van der Waals, and steric interactions relevant to molecular recognition. Optical properties were investigated via time-dependent DFT (TD-B3LYP/6-311 + + G(d,p)) calculations considering the lowest 20 singlet excited states. The computed excitation energies and oscillator strengths were convoluted using a Lorentzian function with 0.10 eV bandwidth to obtain the simulated UV–Vis absorption spectrum. For comparison with experimental analogs, theoretical FT-IR frequencies obtained from harmonic analysis were scaled by a factor of 0.967 to correct for anharmonic effects and directly compared with literature spectra of structurally related heterocycles [\u003cspan additionalcitationids=\"CR23\" citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e–\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. The overall computational approach provides a consistent description of the equilibrium geometry, electronic configuration, vibrational stability, and photophysical behavior of TTCA, thereby establishing a reliable framework for subsequent structure–property analysis [\u003cspan additionalcitationids=\"CR26\" citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e–\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. Statistical equations were used to quantify the agreement theoretical spectroscopic values, and the calculated results is summarized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e-spectroscopic characterization section [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e].\u003c/p\u003e\u003cp\u003e\u003cimg 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\" width=\"724\" height=\"404\"\u003e\u003c/p\u003e"},{"header":"Result and Discussion","content":"\u003ch2\u003eGeometry Optimization\u003c/h2\u003e\u003cp\u003eThe optimized structure of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) obtained from DFT calculations is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The molecule exhibits an almost planar configuration, suggesting strong π-conjugation between the triazole and thiophene rings. This coplanarity enhances intramolecular charge delocalization, resulting in higher electronic stability. The carboxylic acid group, attached at the 2-position of the thiophene ring, forms a potential intramolecular hydrogen bond with the neighboring nitrogen atom of the triazole ring. Such interactions stabilize the overall geometry and contribute to the rigidity of the molecular backbone. The theoretical and experimental correlation coefficients for spectral parameters are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, confirming the consistency of the computed structure.\u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eStatistical measures of agreement theoretical data\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"3\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eProperty\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eTheoretical Values\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eNote\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eFT-IR (cm⁻¹)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e3420 (O–H), 1720 (C = O), 1610 (C = N/C = C), 1450–1000 (C–O, C–N), 800–600 (C–H bend)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eCharacteristic vibrational modes from DFT\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eNMR (δ, ppm)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e13.0 (–COOH), 8.8 (Triazole-H), 7.9–8.1 (Thiophene-H)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eProton chemical shifts predicted by DFT\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eUV–Vis (λmax, nm)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e720 (HOMO→LUMO, π→π*), 550 (HOMO–1→LUMO), 470 \u0026amp; 360 (n→π*)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eStrong absorption in 500–750 nm region\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eBand Gap (eV)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e3.1 (HOMO–LUMO), 1.7 (Optical, TDDFT)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eIndicates stability and photoactivity\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e\u003ch3\u003eBand Gap Energy (BG)\u003c/h3\u003e\u003cp\u003eThe spatial distributions of the frontier orbitals are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The HOMO is mainly localized on the sulfur and nitrogen atoms of the heteroaromatic rings, while the LUMO extends over the conjugated π-system, indicating an efficient intramolecular charge-transfer pathway. The computed HOMO–LUMO energy gap (3.13 eV) implies moderate chemical hardness and significant stability. Global reactivity descriptors (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) reveal a balance between electron-donating and electron-accepting capabilities. The calculated ionization potential and electron affinity values indicate that TTCA is electronically stable yet capable of undergoing photoinduced charge redistribution, consistent with its potential optoelectronic functionality.\u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eGlobal Reactivity Descriptors of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) computed at the B3LYP/6-311 + + G(d,p) level\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"3\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eDescriptor\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eCalculated value (eV)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eInterpretation\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eIonization potential\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1.67\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eResistance to electron removal; high IP → chemical stability\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eElectron affinity\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e–1.46\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eElectron-accepting tendency\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eEnergy gap\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e3.13\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eDetermines chemical reactivity and kinetic stability\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eChemical hardness\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1.55\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eResistance to charge transfer\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eChemical softness\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e0.32\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eInverse of hardness; polarizability indicator\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eElectronegativity\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e–0.10\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eElectron-attracting power\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eElectrophilicity index\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e0.003\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eGlobal electron-accepting ability\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e\u003ch3\u003eFT-IR spectrum Spectroscopy\u003c/h3\u003e\u003cp\u003eThe simulated FT-IR spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e) shows distinct vibrational bands corresponding to the functional groups in TTCA. The broad absorption near 3400–3100 cm⁻¹ arises from the O–H stretching vibration of the carboxylic acid, confirming hydrogen-bond involvement. The band around 1700 cm⁻¹ corresponds to C = O stretching, while absorptions at 1610 cm⁻¹ and 1450–1000 cm⁻¹ reflect C = N, C = C, and C–O bond vibrations. These features confirm the triazole–thiophene framework and follow previous DFT vibrational studies of heterocyclic systems [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e\u003ch3\u003eNuclear Magnetic Resonance Spectroscopy\u003c/h3\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e displays the computed ¹H NMR spectrum, which shows three proton environments. The carboxylic proton resonates around δ ≈ 13.0 ppm, the triazole proton near δ ≈ 8.8 ppm, and the thiophene protons between δ ≈ 7.9–8.1 ppm. The downfield shift of the –COOH proton confirms its involvement in intramolecular hydrogen bonding. These results agree with chemical shift trends reported for structurally related aromatic acids and confirm the reliability of the B3LYP/6-311 + + G(d,p) approach for predicting magnetic shielding parameters [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e].\u003c/p\u003e\u003ch2\u003eDensity of States (DOS) and OPDOS\u003c/h2\u003e\u003cp\u003eThe TDOS/OPDOS plots (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e) reveal repeated π-bonding contributions in the valence manifold and anti-bonding features near the frontier orbitals, consistent with the nucleophilic and electrophilic sites identified in the MEP analysis. A dense distribution of virtual states is observed in the conduction band, with the OPDOS suggesting strong charge-transfer potential. Different computational approaches yield different energy gap values. The HOMO–LUMO separation extracted from frontier orbital analysis (Figs.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e) is approximately 3.1 eV, representing the electronic band gap at the DFT ground-state level. The ~ 5.4 eV value observed in the TDOS/OPDOS profile corresponds to the onset of higher-lying virtual states, which should not be directly compared with the fundamental HOMO–LUMO difference. Meanwhile, TDDFT simulations predict an intense optical transition around 720 nm (~ 1.7 eV) (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e), which reflects the optical band gap accessible under photoexcitation. These distinctions clarify that TTCA exhibits a moderate electronic band gap (~ 3.1 eV) but pronounced photoactivity at lower optical excitation energies, making it a promising candidate for optoelectronic and sensing applications.\u003c/p\u003e\u003ch3\u003eUV–Visible Spectral Properties\u003c/h3\u003e\u003cp\u003eThe simulated UV–Vis absorption profile (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e) shows a primary absorption peak at ~ 720 nm, assigned to the π → π* HOMO → LUMO transition. Additional transitions at 550 nm and 470 nm correspond to higher-lying π → π* and n → π* excitations, respectively. These bands signify extended π-conjugation and suggest that TTCA can absorb visible light, which may render it suitable for optoelectronic and sensing applications. Similar photoabsorption enhancement through doping or substitution has been reported in other heteroaromatic frameworks [\u003cspan additionalcitationids=\"CR33\" citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e–\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e].\u003c/p\u003e\u003ch3\u003eMolecular Electrostatic Potential (MEP)\u003c/h3\u003e\u003cp\u003eThe MEP surface (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e) depicts regions of electron density concentration and depletion. The most negative potential is localized over the carbonyl oxygens (O₇, O₈), identifying them as potential coordination sites, whereas the acidic hydrogen of the –COOH group exhibits strong electropositive potential. The sulfur atom of the thiophene ring and the nitrogen atoms of the triazole contribute moderately negative regions, suggesting possible participation in weak donor–acceptor interactions. This charge distribution supports the molecule’s dual character as a ligand and an electron-transfer mediator [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e].\u003c/p\u003e\u003ch2\u003eNon-Covalent Interactions (NCI)\u003c/h2\u003e\u003cp\u003eReduced density gradient (RDG) analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e) was performed to visualize intramolecular weak interactions. Green isosurfaces indicate van der Waals contacts, while small blue regions correspond to hydrogen bonds between the hydroxyl hydrogen and nearby oxygen or nitrogen atoms. These weak interactions enhance molecular stability and influence packing behavior. The RDG features agree with previous Hirshfeld and RDG studies conducted on aromatic carboxylic acids, validating the predicted non-covalent interaction pattern [\u003cspan additionalcitationids=\"CR38\" citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e–\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e].\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn this study, the molecular geometry, electronic configuration, and spectroscopic characteristics of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) were systematically examined through DFT and TD-DFT computations. The optimized structure obtained at the B3LYP/6-311\u0026thinsp;+\u0026thinsp;+\u0026thinsp;G(d,p) level revealed a nearly planar π-conjugated skeleton, stabilized by intramolecular hydrogen bonding. The HOMO\u0026ndash;LUMO gap of approximately 3.1 eV confirms the molecule\u0026rsquo;s electronic stability, while the optical transition energy of 1.7 eV highlights its visible-light activity. The simulated FT-IR and NMR spectra successfully reproduced the characteristic vibrational and chemical-shift features of the triazole, thiophene, and carboxyl functional groups, validating the computational approach. The UV\u0026ndash;Vis analysis revealed strong π\u0026rarr;π* transitions around 720 nm, suggesting efficient electronic delocalization and possible use in optoelectronic devices. The DOS and OPDOS profiles further emphasized charge delocalization across the heterocyclic system, while the MEP map identified oxygen and nitrogen atoms as preferred nucleophilic and coordination centers. Non-covalent interaction (NCI) and RDG analyses indicated weak hydrogen-bonding and van der Waals interactions that reinforce molecular planarity and stability. These interactions, combined with a moderate band gap and broad absorption profile, underline TTCA\u0026rsquo;s suitability for applications in coordination chemistry, sensor technology, and photoactive organic materials. The present work provides a comprehensive theoretical perspective on the structural, electronic, and optoelectronic features of TTCA. The obtained insights not only advance understanding of heteroaromatic charge-transfer systems but also pave the way for future studies on TTCA-based coordination complexes and functional materials optimized for optoelectronic and sensing purposes.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003ch2\u003eEthics approval\u003c/h2\u003e\u003cp\u003eThis article does not contain any studies with human participants or animals performed by the author.\u003c/p\u003e\u003c/p\u003e\u003cp\u003e\u003cstrong\u003eConsent to participate\u003c/strong\u003e\u003cp\u003eNot applicable.\u003c/p\u003e\u003c/p\u003e\u003cp\u003e\u003cstrong\u003eConsent to publish\u003c/strong\u003e\u003cp\u003eThe author declares that the work is original, has not been published previously, and is not under consideration for publication elsewhere.\u003c/p\u003e\u003c/p\u003e\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003cp\u003eThe author declares no competing interests.\u003c/p\u003e\u003c/p\u003e\u003ch2\u003eFunding\u003c/h2\u003e\u003cp\u003eThe author received no financial support for the research, authorship, and/or publication of this article.\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eThe author confirms sole responsibility for study conception, design, data collection, analysis, interpretation of results, and manuscript preparation.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e\u003cp\u003eNot applicable.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eThe datasets generated and/or analysed during the current study are available from the corresponding author on reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eCoelho Dias IF, Santi C, Sancineto L (2025) Recent advances in the chemistry of 5- and 6-membered selenacycles and selenaheterocycles. \u003cem\u003eAsian Journal of Organic Chemistry\u003c/em\u003e e202500093. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/ajoc.202500093\u003c/span\u003e\u003cspan address=\"10.1002/ajoc.202500093\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eMar\u0026iacute;n M, L\u0026oacute;pez M, Gallego-Yerga L, \u0026Aacute;lvarez R, Pel\u0026aacute;ez R (2024) Experimental structure-based drug design (SBDD) applications for anti-leishmanial drugs: a paradigm shift? 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Y\u0026uuml;z\u0026uuml;nc\u0026uuml; Yıl \u0026Uuml;niversitesi Fen Bilimleri Enstit\u0026uuml;s\u0026uuml; Dergisi 29(3):854\u0026ndash;867. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.53433/yyufbed.1413089\u003c/span\u003e\u003cspan address=\"10.53433/yyufbed.1413089\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eKebiroğlu MH (2025) Integrated DFT mapping of structural, thermochemical, non-covalent, and toxicological profiles of 2-(tetrahydro-2H-pyran-4-ylmethoxy)-4-pyrimidinecarboxylic acid (THPMPCA). \u003cem\u003eArabian Journal for Science and Engineering\u003c/em\u003e (online first):1\u0026ndash;10. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s13369-025-10658-0\u003c/span\u003e\u003cspan address=\"10.1007/s13369-025-10658-0\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-computer-aided-molecular-design","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jcam","sideBox":"Learn more about [Journal of Computer-Aided Molecular Design](http://link.springer.com/journal/10822)","snPcode":"10822","submissionUrl":"https://submission.nature.com/new-submission/10822/3","title":"Journal of Computer-Aided Molecular Design","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid, Density functional theory (DFT), Time-dependent DFT (TD-DFT), Molecular electrostatic potential (MEP), Spectroscopy (FT-IR, NMR, UV–Vis)","lastPublishedDoi":"10.21203/rs.3.rs-8029749/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8029749/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe structural, spectroscopic, and electronic characteristics of 5-(1H-1,2,4-triazol-1-yl)-2-thiophenecarboxylic acid (TTCA) were investigated using DFT and TD-DFT approaches at the B3LYP/6-311\u0026thinsp;+\u0026thinsp;+\u0026thinsp;G(d,p) level. Geometry optimization confirmed a planar π-conjugated structure stabilized by intramolecular hydrogen bonding. The computed HOMO\u0026ndash;LUMO energy gap (3.13 eV) and optical transition energy (1.7 eV) revealed chemical stability and visible-light photoactivity. Simulated FT-IR, NMR, and UV\u0026ndash;Vis spectra agreed with experimental analogs, validating the theoretical approach. Global reactivity descriptors (IP, EA, η, S, χ, ω) further elucidated the charge-transfer capacity and electronic softness of the molecule. Density of states, molecular electrostatic potential, and non-covalent interaction analyses revealed strong π-delocalization and donor\u0026ndash;acceptor interaction within the triazole\u0026ndash;thiophene framework. These results provide new theoretical insights into the optoelectronic tunability of heteroaromatic systems, highlighting TTCA as a promising scaffold for future coordination and photoactive material design.\u003c/p\u003e","manuscriptTitle":"Theoretical Insights into the Optoelectronic and Charge-Transfer Characteristics of 5-(1H- 1,2,4-triazol-1-yl)-2-thiophenecarboxylic Acid","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-11-24 09:34:17","doi":"10.21203/rs.3.rs-8029749/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-12-08T21:08:53+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-12-08T19:55:03+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-24T14:35:18+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"174971721331700535059658369324908880674","date":"2025-11-15T03:41:33+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"27907589610830339575654417651281762027","date":"2025-11-12T13:45:27+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-11-12T13:34:13+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-11-12T00:27:32+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-11-05T03:17:11+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Computer-Aided Molecular Design","date":"2025-11-04T14:02:39+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-computer-aided-molecular-design","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jcam","sideBox":"Learn more about [Journal of Computer-Aided Molecular Design](http://link.springer.com/journal/10822)","snPcode":"10822","submissionUrl":"https://submission.nature.com/new-submission/10822/3","title":"Journal of Computer-Aided Molecular Design","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"e019494b-862b-424d-955e-10df7d79f091","owner":[],"postedDate":"November 24th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-01-12T16:07:17+00:00","versionOfRecord":{"articleIdentity":"rs-8029749","link":"https://doi.org/10.1007/s10822-025-00752-8","journal":{"identity":"journal-of-computer-aided-molecular-design","isVorOnly":false,"title":"Journal of Computer-Aided Molecular Design"},"publishedOn":"2026-01-10 15:59:32","publishedOnDateReadable":"January 10th, 2026"},"versionCreatedAt":"2025-11-24 09:34:17","video":"","vorDoi":"10.1007/s10822-025-00752-8","vorDoiUrl":"https://doi.org/10.1007/s10822-025-00752-8","workflowStages":[]},"version":"v1","identity":"rs-8029749","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8029749","identity":"rs-8029749","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}