Synthesis, Spectroscopic Characterization Techniques, and Functional Applications of Selenium Heterocycles

Abstract

The paper reviews the unique chemical properties of selenium, focusing on selenium-containing heterocycles and organoselenium chemistry. The present study undertakes a critical examination of synthetic strategies, ranging from classical nucleophilic selenation and transition-metal catalysis to emerging photo-redox and electrochemical approaches. The text goes on to highlight advanced characterisation techniques, with particular reference to the combination of ⁷⁷Se NMR spectroscopy with DFT calculations and single-crystal X-ray diffraction for structural elucidation. The functional applications of these compounds are the subject of extensive discussion, including their role in enhancing the performance of sustainable organic photovoltaic (OPV) materials for renewable energy conversion, and their potential in biomedicine as TrxR inhibitors for cancer therapy and as photosensitizers in antibacterial applications. The present study places particular emphasis on the contribution of selenium-containing heterocycles to improving the power conversion efficiency (PCE) of solar devices. Finally, the review outlines future research directions and common challenges in this field, such as enhancing the sustainability of catalytic processes and addressing biosafety concerns associated with selenium-based reagents.

Keywords

Selenium heterocyclic compounds / Photocatalytic selenation / Electrochemical synthesis / Selenium NMR spectroscopy / Organic photovoltaic materials / Sustainable energy materials / TrxR inhibitors / Benzoselenazoles

Statement of the Use of Generative AI and AI-Assisted Technologies in the Writing Process

During the writing of this paper, the author used Deepseek, Doubao and DeepL to optimise keywords for literature searches, proofread English grammar, and summarise and express literature data, with the aim of enhancing the paper’s readability and fluency. The author independently completed the core research design, data collection and analysis, experimental validation, and conclusion derivation. AI-generated content underwent comprehensive verification and revision to ensure its accuracy and academic compliance. The author assumes full responsibility for all content in this paper.

Acknowledgments

The authors would like to thank their colleagues for helpful discussions and support throughout this work. The authors also appreciate the administrative and logistical assistance that facilitated the completion of this study.

Author Contributions

Conceptualization, P.L.; Methodology, J.L.(Jiayi Lin) and X.Z.; Validation, P.L., J.L.(Jiayi Lin) and H.D.N.; Formal Analysis, Y.F. and Z.W.; Investigation, P.L., J.L. (Jiayi Lin) and H.D.N.; Resources, J.L.(Jianhui Li); Data Curation, J.L.(Jiayi Lin) and X.Z.; Writing—Original Draft Preparation, P.L.; Writing—Review & Editing, J.L.(Jiayi Lin) and Y.F.; Visualization, M.L. and Y.F.; Supervision, R.Z. and Z.W.; Project Administration, J.L.(Jianhui Li) and M.L.

Ethics Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data sharing is not applicable to this article, as no new data were created in this study.

Funding

This work was funded by the National Natural Science Foun dation of China (22579056), the Guangdong Provincial Interna tional Joint Research Center for Energy Storage Materials (2023A0505090009), and the Science and Technology Planning Project of Guangzhou City (2023B03J1278) and youth Teacher Research and Cultivation Fund of South China Normal University (Project No. 671866), presided over, 30,000 yuan.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

References

[1] Patwardhan RS, Sharma D, Sandur SK. Thioredoxin Reductase: An Emerging Pharmacologic Target for Radiosensitization of Cancer. Transl. Oncol. 2022, 17, 101341. doi:10.1016/j.tranon.2022.101341.

[2] Gencheva R, Arnér ESJ. Thioredoxin Reductase Inhibition for Cancer Therapy. Annu. Rev. Pharmacol. Toxicol. 2022, 62, 177-196. doi:10.1146/annurev-pharmtox-052220-102509.

[3] De Darwent BB. Bond Dissociation Energies in Simple Molecules. NSRDS-NBS 1970, 31, 1-52.

[4] Milen M, Szabó T. Recent Developments in the Synthesis of Se-Heterocycles Applying Elemental Selenium (Microreview). Chem. Heterocycl. Compd. 2019, 55, 936-938. doi:10.1007/s10593-019-02559-6.

[5] Swaroop TR, Shivaprasad CM, Preetham R, Sadashiva MP, Rangappa KS. Developments in the Electrochemical Synthesis of Thia-Heterocycles. Phosphorus Sulfur Silicon Relat. Elem. 2022, 197, 891-898. doi:10.1080/10426507.2022.2057498.

[6] Patel A, Narkhede N, Singh S, Pathan S. Keggin-Type Lacunary and Transition Metal Substituted Polyoxometalates as Heterogeneous Catalysts: A Recent Progress. Catal. Rev. 2016, 58, 337-370. doi:10.1080/01614940.2016.1171606.

[7] Raabe J-C, Esser T, Jameel F, Stein M, Albert J, Poller MJ. Study on the Incorporation of Various Elements into the Keggin Lacunary-Type Phosphomolybdate [PMo₉O₃₄]^9- and Subsequent Purification of the Polyoxometalates by Nanofiltration. Inorg. Chem. Front. 2023, 10, 4854-4868. doi:10.1039/D3QI00937H.

[8] Wang Z, Xin X, Zhang M, Li Z, Lv H, Yang G-Y. Recent Advances of Mixed-Transition-Metal-Substituted Polyoxometalates. Sci. China Chem. 2022, 65, 1515-1525. doi:10.1007/s11426-022-1276-4.

[9] Yang G, Liu Y, Wei Y. Application of Polyoxometalates in Biomass Conversion. Coord. Chem. Rev. 2024, 521, 216172. doi:10.1016/j.ccr.2024.216172.

[10] Cupp-Sutton K, Ashby M. Biological Chemistry of Hydrogen Selenide. Antioxidants 2016, 5, 42. doi:10.3390/antiox5040042.

[11] Hou W, Xu H. Incorporating Selenium into Heterocycles and Natural Products—From Chemical Properties to Pharmacological Activities. J. Med. Chem. 2022, 65, 4436-4456. doi:10.1021/acs.jmedchem.1c01859.

[12] Song C-C, Du F-S, Li Z-C. Oxidation-Responsive Polymers for Biomedical Applications. J. Mater. Chem. B 2014, 2, 3413-3426. doi:10.1039/C3TB21725F.

[13] Martynov AV. Elemental Selenium in the Synthesis of Selenaheterocycles. Inorganics 2023, 11, 727. doi:10.3390/inorganics11070287.

[14] Marsh AV, Heeney M. Conjugated Polymers Based on Selenophene Building Blocks. Polym. J. 2023, 55, 375-385. doi:10.1038/s41428-022-00731-y.

[15] Hasimujiang B, Zhu J, Xu W, Wang H, Hu X, Ruan Z. Solvent-Regulated Electrochemical Selenylation and Deuteration of Alkynyl Aryl Ketones: Chemoselective Synthesis of 3-Selenylated Chromones and Deutero-Selenylated Chalcones. Adv. Synth. Catal. 2023, 365, 2929-2935. doi:10.1002/adsc.202300512.

[16] Hashmi SZ, Bareth D, Dwivedi J, Kishore D, Alvi PA. Green Advancements towards the Electrochemical Synthesis of Heterocycles. RSC Adv. 2024, 14, 18192-18246. doi:10.1039/D4RA02812K.

[17] Penteado F, Peglow TJ, Silva MS, Perin G, Lenardão EJ. Greening the Synthesis of Selenium-Containing Heterocycles: Recent Efforts and Advances. Curr. Opin. Green Sustain. Chem. 2020, 26, 100372. doi:10.1016/j.cogsc.2020.100372.

[18] Jiang J-M, Raghunath P, Lin H-K, Lin Y-C, Lin MC, Wei K-H. Location and Number of Selenium Atoms in Two-Dimensional Conjugated Polymers Affect Their Band-Gap Energies and Photovoltaic Performance. Macromolecules 2014, 47, 7070-7080. doi:10.1021/ma501720k.

[19] Mukherjee AJ, Zade SS, Singh HB, Sunoj RB. Organoselenium Chemistry: Role of Intramolecular Interactions. Chem. Rev. 2010, 110, 4357-4416. doi:10.1021/cr900352j.

[20] Zhou T, Szostak M. Palladium-Catalyzed Cross-Couplings by C-O Bond Activation. Catal. Sci. Technol. 2020, 10, 5702-5739. doi:10.1039/D0CY01159B.

[21] Protti S, Fagnoni M. Recent Advances in Light-Induced Selenylation. ACS Org. Inorg. Au 2022, 2, 455-463. doi:10.1021/acsorginorgau.2c00033.

[22] Shaaban S, Ba-Ghazal H, Al-Faiyz YS, Al-Karmalawy AA, Amri N, Youssef I. Recent Advances in the Synthesis of Organoselenium Heterocycle Conjugates. Tetrahedron 2024, 157, 133957. doi:10.1016/j.tet.2024.133957.

[23] Sonego JM, De Diego SI, Szajnman SH, Gallo-Rodriguez C, Rodriguez JB. Organoselenium Compounds: Chemistry and Applications in Organic Synthesis. Chem. A Eur. J. 2023, 29, e202300030. doi:10.1002/chem.202300030.

[24] Klayman DL, Griffin TS. Reaction of Selenium with Sodium Borohydride in Protic Solvents. A Facile Method for the Introduction of Selenium into Organic Molecules. J. Am. Chem. Soc. 1973, 95, 197-199. doi:10.1021/ja00782a034.

[25] Old DW, Wolfe JP, Buchwald SL. A Highly Active Catalyst for Palladium-Catalyzed Cross-Coupling Reactions:  Room-Temperature Suzuki Couplings and Amination of Unactivated Aryl Chlorides. J. Am. Chem. Soc. 1998, 120, 9722-9723. doi:10.1021/ja982250+.

[26] Long H, Zhao S, Jian C, Wu X, Lu F, Liao M, et al. Carbene-Catalyzed Enantioselective Seleno-Michael Addition as Access to Antimicrobial Active Se-Containing Heterocycles. Sci. China Chem. 2024, 67, 2199-2205. doi:10.1007/s11426-023-1909-5.

[27] Godoi B, Schumacher RF, Zeni G. Synthesis of Heterocycles via Electrophilic Cyclization of Alkynes Containing Heteroatom. Chem. Rev. 2011, 111, 2937-2980. doi:10.1021/cr100214d.

[28] Chao MN, Storey M, Li C, Rodríguez MG, Di Salvo F, Szajnman SH, et al. Selenium-Containing Analogues of WC-9 Are Extremely Potent Inhibitors of Trypanosoma Cruzi Proliferation. Bioorg. Med. Chem. 2017, 25, 6435-6449. doi:10.1016/j.bmc.2017.10.016.

[29] Chao MN, Lorenzo-Ocampo MV, Szajnman SH, Docampo R, Rodriguez JB. Further Insights of Selenium-Containing Analogues of WC-9 against Trypanosoma Cruzi. Bioorg. Med. Chem. 2019, 27, 1350-1361. doi:10.1016/j.bmc.2019.02.039.

[30] Garud DR, Koketsu M, Ishihara H. Isoselenocyanates: A Powerful Tool for the Synthesis of Selenium-Containing Heterocycles. Molecules 2007, 12, 504-535. doi:10.3390/12030504.

[31] Fors BP, Buchwald SL. A Multiligand Based Pd Catalyst for C-N Cross-Coupling Reactions. J. Am. Chem. Soc. 2010, 132, 15914-15917. doi:10.1021/ja108074t.

[32] Marion N, Ecarnot EC, Navarro O, Amoroso D, Bell A, Nolan SP. (IPr)Pd(Acac)Cl: An Easily Synthesized, Efficient, and Versatile Precatalyst for C-N and C-C Bond Formation. J. Org. Chem. 2006, 71, 3816-3821. doi:10.1021/jo060190h.

[33] Christmann U, Vilar R, White AJP, Williams DJ. Synthesis of two novel dinuclear palladium(i) complexes and studies of their catalytic activity in amination reactions. Chem. Commun. 2004, 11, 1294-1295. doi:10.1039/B402283A.

[34] Badshah G, Gomes CMB, Ali S, Luz EQ, Silvério GL, Santana FS, et al. Palladium-Catalyzed Direct Selanylation of Chalcogenophenes and Arenes Assisted by 2-(Methylthio)Amide. J. Org. Chem. 2023, 88, 14033-14047. doi:10.1021/acs.joc.3c01577.

[35] Mandal A, Sahoo H, Baidya M. Copper-Catalyzed 8-Aminoquinoline-Directed Selenylation of Arene and Heteroarene C-H Bonds. Org. Lett. 2016, 18, 3202-3205. doi:10.1021/acs.orglett.6b01420.

[36] Fang Y, Rogge T, Ackermann L, Wang S-Y, Ji S-J. Nickel-Catalyzed Reductive Thiolation and Selenylation of Unactivated Alkyl Bromides. Nat. Commun. 2018, 9, 2240. doi:10.1038/s41467-018-04646-2.

[37] Rios EAM, Gomes CMB, Silvério GL, Luz EQ, Ali S, D’Oca CDRM, et al. Silver-Catalyzed Direct Selanylation of Indoles: Synthesis and Mechanistic Insights. RSC Adv. 2023, 13, 914-925. doi:10.1039/D2RA06813C.

[38] Prier CK, Rankic DA, MacMillan DWC. Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis. Chem. Rev. 2013, 113, 5322-5363. doi:10.1021/cr300503r.

[39] Cheung KPS, Sarkar S, Gevorgyan V. Visible Light-Induced Transition Metal Catalysis. Chem. Rev. 2022, 122, 1543-1625. doi:10.1021/acs.chemrev.1c00403.

[40] Jiang S, Leng Y, Wang P, Sui K, Ma N, Wu Y. Visible-Light-Induced Regioselective Selenohydroxylation of Enamine Amides with Diaryl Diselenides. Eur. J. Org. Chem. 2024, 27, e202400600. doi:10.1002/ejoc.202400600.

[41] Dalberto BT, Schneider PH. Photoinduced Metal-Free α-Selenylation of Ketones. RSC Adv. 2020, 10, 10502-10509. doi:10.1039/D0RA00802H.

[42] Hou H, Sun Y, Pan Y, Yu H, Han Y, Shi Y, et al. Visible-Light Mediated Diarylselenylative Cyclization of 1,6-Enynes. J. Org. Chem. 2021, 86, 1273-1280. doi:10.1021/acs.joc.0c02529.

[43] Zuo H-D, Chen X, Zhang Y, Liu J-W, Yan S-H, Li G, et al. Photocatalytic Thio/Selenosulfonylation-Bicyclization of Indole-Tethered 1,6-Enynes Leading to Substituted Benzo[c]pyrrolo[1,2,3-lm]carbazoles. Org. Lett. 2024, 26, 3828-3833. doi:10.1021/acs.orglett.4c00981.

[44] Song Z-J, Bao Y, Sun Y-J, Yan S, Zhang Y, Li G, et al. Photoinduced Alkylsulfonylation and Cyanoalkylsulfonylation of Morita-Baylis-Hillman Adducts via Multicomponent Insertion of Sulfur Dioxide. J. Org. Chem. 2024, 89, 4877-4887. doi:10.1021/acs.joc.4c00052.

[45] Wang J-Y, Zhang S, Tang Y, Yan S, Li G. Copper-Catalyzed Annulation-Trifluoromethyl Functionalization of Enynones. Org. Lett. 2023, 25, 2509-2514. doi:10.1021/acs.orglett.3c00679.

[46] Wang J-Y, Zhang S, Yuan Q, Li G, Yan S. Catalytic Radical-Triggered Annulation/Iododifluoromethylation of Enynones for the Stereospecific Synthesis of 1-Indenones. J. Org. Chem. 2023, 88, 8532-8541. doi:10.1021/acs.joc.3c00471.

[47] Hoppe C-F, Arndt S, Stenner P. Electrifying Organic Synthesis. Chem. Ing. Tech. 2022, 94, 1224-1225. doi:10.1002/cite.202255021.

[48] Jiao K-J, Xing Y-K, Yang Q-L, Qiu H, Mei T-S. Site-Selective C-H Functionalization via Synergistic Use of Electrochemistry and Transition Metal Catalysis. Acc. Chem. Res. 2020, 53, 300-310. doi:10.1021/acs.accounts.9b00603.

[49] Xiong P, Xu H-C. Chemistry with Electrochemically Generated N-Centered Radicals. Acc. Chem. Res. 2019, 52, 3339-3350. doi:10.1021/acs.accounts.9b00472.

[50] Yan M, Kawamata Y, Baran PS. Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance. Chem. Rev. 2017, 117, 13230-13319. doi:10.1021/acs.chemrev.7b00397.

[51] Ai Z, Xiao J, Li Y, Guo B, Du Y, Zhao K. Metal-Free Synthesis of 3-Chalcogenyl Chromones from Alkynyl Aryl Ketones and Diorganyl Diselenides/Disulfides Mediated by PIFA. Org. Chem. Front. 2020, 7, 3935-3940. doi:10.1039/D0QO01175D.

[52] Godoi B, Sperança A, Bruning CA, Back DF, Menezes PH, Nogueira CW, et al. Iron(III) Chloride/Diorganyl Diselenides-Promoted Regioselective Cyclization of Alkynyl Aryl Ketones: Synthesis of 3-Organoselenyl Chromenones under Ambient Atmosphere. Adv. Synth. Catal. 2011, 353, 2042-2050. doi:10.1002/adsc.201100189.

[53] Guan Z, Wang Y, Wang H, Huang Y, Wang S, Tang H, et al. Electrochemical Oxidative Cyclization of Olefinic Carbonyls with Diselenides. Green Chem. 2019, 21, 4976-4980. doi:10.1039/C9GC02665G.

[54] Cheng Z, Gu Q, Zeng X. Synthesis of Benzoselenophenes and Benzothiophenes via Electrochemical Oxidative Seleno(Thio)Cyanation/Cyclization Tandem Reaction of Enamides. Asian J. Org. Chem. 2023, 12, e202300461. doi:10.1002/ajoc.202300461.

[55] Hu L, Zhang J, Li M, Feng Y, Lu F. Electrochemical Oxidative Radical Cascade Cyclization of Dienes and Diselenides towards the Synthesis of Seleno-Benzazepines. RSC Adv. 2024, 14, 12556-12560. doi:10.1039/D4RA01914H.

[56] Yang J, Gao W, Teng Y, Yu L, Huang K, Li Q, et al. Electrochemically Driven Tandem Cyclization Reaction of Unsaturated Sulfoximines with Diselenides. Eur. J. Org. Chem. 2024, 27, e202300927. doi:10.1002/ejoc.202300927.

[57] Xu W, Zheng C, Chen M, Deng X, Zhang L, Lei X, et al. Modular Synthesis of Bioactive Selenoheterocycles for Efficient Cancer Therapy via Electrochemical Selenylation/Cyclization. J. Med. Chem. 2025, 68, 6339-6360. doi:10.1021/acs.jmedchem.4c02724.

[58] Lassaletta JM. Spotting Trends in Organocatalysis for the next Decade. Nat. Commun. 2020, 11, 3787. doi:10.1038/s41467-020-17600-y.

[59] Gautam N, Maji S, Bhattacharyya K, Mandal SK. Transition Metal-Mimicking Relay Catalysis by a Low-Valent Phosphorus Compound. J. Am. Chem. Soc. 2024, 146, 16743-16752. doi:10.1021/jacs.4c04376.

[60] Xu K, Huang P, Wu Y, Liu T, Shao N, Zhao L, et al. Engineered Selenium/Human Serum Albumin Nanoparticles for Efficient Targeted Treatment of Parkinson’s Disease via Oral Gavage. ACS Nano 2023, 17, 19961-19980. doi:10.1021/acsnano.3c05011.

[61] An F-F, Zhang X-H. Strategies for Preparing Albumin-Based Nanoparticles for Multifunctional Bioimaging and Drug Delivery. Theranostics 2017, 7, 3667-3689. doi:10.7150/thno.19365.

[62] Pérez-López AM, Belsom A, Fiedler L, Xin X, Rappsilber J. Dual-Bioorthogonal Catalysis by a Palladium Peptide Complex. J. Med. Chem. 2023, 66, 3301-3311. doi:10.1021/acs.jmedchem.2c01689.

[63] Wang C, Li H, Bürgin TH, Wenger OS. Cage Escape Governs Photoredox Reaction Rates and Quantum Yields. Nat. Chem. 2024, 16, 1151-1159. doi:10.1038/s41557-024-01482-4.

[64] Sun K, Qian Y, Li D, Jiang H. Reticular Materials for Photocatalysis. Adv. Mater. 2024, 2411118. doi:10.1002/adma.202411118.

[65] Shetty M, Walton A, Gathmann SR, Ardagh MA, Gopeesingh J, Resasco J, et al. The Catalytic Mechanics of Dynamic Surfaces: Stimulating Methods for Promoting Catalytic Resonance. ACS Catal. 2020, 10, 12666-12695. doi:10.1021/acscatal.0c03336.

[66] Pasindu V, Munaweera I. Harnessing Atomic-Scale Defect Engineering in 2D Photocatalysts: Synergistic Integration of Nanocomposite Architectures for Bandgap Tuning and Charge Transfer Optimization. RSC Adv. 2025, 15, 34191-34210. doi:10.1039/D5RA05074J.

[67] Lgaz H, Messali M, Ebenso EE, Lee H. Defect-Activated Anatase TiO₂ Surfaces for Enhanced Capture of Bisphenol S and Sulfolane: A Coupled DFT and SCC-DFTB Analysis. Appl. Surf. Sci. 2025, 706, 163601. doi:10.1016/j.apsusc.2025.163601.

[68] Yang Q, Wang Y-H, Qiao Y, Gau M, Carroll PJ, Walsh PJ, et al. Photocatalytic C-H Activation and the Subtle Role of Chlorine Radical Complexation in Reactivity. Science 2021, 372, 847-852. doi:10.1126/science.abd8408.

[69] Buglioni L, Raymenants F, Slattery A, Zondag SDA, Noël T. Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry. Chem. Rev. 2022, 122, 2752-2906. doi:10.1021/acs.chemrev.1c00332.

[70] Heredia AA, Bouchet LM, Castro-Godoy WD, Argüello JE. Synthesis of Organoselenium Compounds Using Electrochemical and Photochemical Methods as Novel Approaches in Organic Chemistry. Tetrahedron 2023, 148, 133667. doi:10.1016/j.tet.2023.133667.

[71] Heard DM, Lennox AJJ. Electrode Materials in Modern Organic Electrochemistry. Angew. Chem. Int. Ed. 2020, 59, 18866-18884. doi:10.1002/anie.202005745.

[72] Buchanan C, Shaheen NA, Williams CK, Messias I, Dean-Kersten B, Kim T, et al. Investigation of Electrode Passivation during Oxidation of a Nitroxide Radical Relevant for Flow Battery Applications. J. Mater. Chem. A 2025, 13, 25363-25374. doi:10.1039/D5TA00481K.

[73] Alzaidi O, Wirth T. Continuous Flow Electroselenocyclization of Allylamides and Unsaturated Oximes to Selenofunctionalized Oxazolines and Isoxazolines. ACS Org. Inorg. Au 2024, 4, 350-355. doi:10.1021/acsorginorgau.4c00008.

[74] Liu D, Liu Z-R, Wang Z-H, Ma C, Herbert S, Schirok H, et al. Paired Electrolysis-Enabled Nickel-Catalyzed Enantioselective Reductive Cross-Coupling between α-Chloroesters and Aryl Bromides. Nat. Commun. 2022, 13, 7318. doi:10.1038/s41467-022-35073-z.

[75] Silva MS, Alves D, Hartwig D, Jacob RG, Perin G, Lenardão EJ. Selenium-NMR Spectroscopy in Organic Synthesis: From Structural Characterization Toward New Investigations. Asian J. Org. Chem. 2021, 10, 91-128. doi:10.1002/ajoc.202000582.

[76] Shankar KB, Rajput JD, Yadav V. Synthesis and Structure Elucidation of 2,6-Dimethyl-3,5-Diphenyl-2H-1,4-Selenazine Using Modern Sophisticated Analytical Techniques. Int. J. Sci. Develop. Res. 2022, 7, 242-249.

[77] Bould J, Londesborough MGS, Tok OL. Experimental and Computational ⁷⁷Se NMR Spectroscopic Study on Selenaborane Cluster Compounds. Inorg. Chem. 2024, 63, 16186-16193. doi:10.1021/acs.inorgchem.4c01890.

[78] Kondrashova SA, Latypov SK. “Finger Prints” of N-Heterocyclic Carbenes, DFT Analysis: Scopes and Limitations. Molecules 2023, 28, 7729. doi:10.3390/molecules28237729.

[79] Rusakov YY, Rusakova IL, Krivdin LB. MP2 Calculation of ⁷⁷Se NMR Chemical Shifts Taking into Account Relativistic Corrections. Magn. Reson. Chem. 2015, 53, 485-492. doi:10.1002/mrc.4226.

[80] Fellowes T, Sani M, White J. Fingerprints of Chalcogen Bonding Revealed Through ⁷⁷Se-NMR. Chem.-A Eur. J. 2024, 30, e202400385. doi:10.26434/chemrxiv-2024-htc2p.

[81] Anghinoni JM, Ferreira SS, Penteado F, Lenardão EJ, Silva MS. ⁷⁷Se and ¹³C NMR Characterization of Selenium Cyanides. Molbank 2022, 2022, M1485. doi:10.3390/M1485.

[82] Rodrigues Silva D, Blokker E, Van Der Schuur JM, Hamlin TA, Bickelhaupt FM. Nature and Strength of Group-14 A-A′ Bonds. Chem. Sci. 2024, 15, 1648-1656. doi:10.1039/D3SC06215E.

[83] Kravchenko EA, Buslaev YA. Electronic Effects of Substitution and Reconstruction of the Coordination Polyhedron in Adducts of Main Group IV Element Halides. Russ. Chem. Rev. 1999, 68, 709-726. doi:10.1070/RC1999v068n09ABEH000497.

[84] Dolgova NV, Nehzati S, Choudhury S, MacDonald TC, Regnier NR, Crawford AM, et al. X-Ray Spectroscopy and Imaging of Selenium in Living Systems. Biochim. Biophys. Acta BBA-Gen. Subj. 2018, 1862, 2383-2392. doi:10.1016/j.bbagen.2018.04.024.

[85] Burguera S, Gomila RM, Bauzá A, Frontera A. Selenoxides as Excellent Chalcogen Bond Donors: Effect of Metal Coordination. Molecules 2022, 27, 8837. doi:10.3390/molecules27248837.

[86] Schwartz P-O, Förtsch S, Vogt A, Mena-Osteritz E, Bäuerle P. Selenophene-Containing Heterotriacenes by a C-Se Coupling/Cyclization Reaction. Beilstein J. Org. Chem. 2019, 15, 1379-1393. doi:10.3762/bjoc.15.138.

[87] Ren S, Wang Z, Zhang W, Ding Y, Yi Z. Donor-Acceptor-Based Organic Polymer Semiconductor Materials to Achieve High Hole Mobility in Organic Field-Effect Transistors. Polymers 2023, 15, 3713. doi:10.3390/polym15183713.

[88] Velusamy A, Chen Y, Lin M, Afraj SN, Liu J, Chen M, et al. Diselenophene-Dithioalkylthiophene Based Quinoidal Small Molecules for Ambipolar Organic Field Effect Transistors. Adv. Sci. 2024, 11, 2305361. doi:10.1002/advs.202305361.

[89] Chen R, Lei F, Jin D, Peng K, Liu Q, Zhong Y, et al. Unraveling the Strength and Nature of Se∙∙∙O Chalcogen Bonds: A Comparative Study of SeF₂ and SeF₄ Interactions with Oxygen-Bearing Lewis Bases. Molecules 2024, 29, 5739. doi:10.3390/molecules29235739.

[90] Ward AT. Molecular Structure of Dilute Vitreous Selenium-Sulfur and Selenium-Tellurium Alloys. J. Phys. Chem. 1970, 74, 4110-4115. doi:10.1021/j100717a019.

[91] Poborchii VV, Fokin AV. Raman and Optical Absorption Spectra of Oriented Se₈ and Se₁₂ Rings Formed in Zeolites: Dependence on the Se Loading Density. Microporous Mesoporous Mater. 2022, 338, 111954. doi:10.1016/j.micromeso.2022.111954.

[92] Kretzschmar J, Jordan N, Brendler E, Tsushima S, Franzen C, Foerstendorf H, et al. Spectroscopic Evidence for Selenium(IV) Dimerization in Aqueous Solution. Dalton Trans. 2015, 44, 10508-10515. doi:10.1039/C5DT00730E.

[93] Ashraf MN, Majeed MI, Nawaz H, Iqbal MA, Iqbal J, Iqbal N, et al. Raman Spectroscopic Characterization of Selenium N-Heterocyclic Carbene Compounds. Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 2022, 270, 120823. doi:10.1016/j.saa.2021.120823.

[94] Younas S, Riaz A, Nawaz H, Majeed MI, Iqbal MA, Rashid N, et al. Characterization of Three Different Benzimidazolium Ligands and Their Organo-Selenium Complexes by Using Density Functional Theory and Raman Spectroscopy. RSC Adv. 2023, 13, 35292-35304. doi:10.1039/D3RA04931K.

[95] Huda NU, Wasim M, Nawaz H, Majeed MI, Javed MR, Rashid N, et al. Synthesis, Characterization, and Evaluation of Antifungal Activity of 1-Butyl-3-hexyl-1H-imidazol-2(3H)-selenone by Surface-Enhanced Raman Spectroscopy. ACS Omega 2023, 8, 36460-36470. doi:10.1021/acsomega.3c05436.

[96] Qin Z, Wang W, Wu Y, Zhan X, Zhang Q. Raman Spectroscopy Studies on Dimethyl Selenium at Pressures of up to 40.6 GPa. J. Raman Spectrosc. 2018, 49, 728-735. doi:10.1002/jrs.5328.

[97] Ali S, Riaz A, Nawaz H, Majeed MI, Iqbal MA, Bhatti HN, et al. Raman Spectral Characterization of Silver Metal-Based Complexes of Different Benzimidazolium Ligands. Spectrochim. Acta. A Mol. Biomol. Spectrosc. 2020, 232, 118162. doi:10.1016/j.saa.2020.118162.

[98] Ali S, Riaz A, Majeed MI, Iqbal MA, Bhatti HN, Rashid N, et al. Raman Spectroscopy along with Principal Component Analysis for the Confirmation of Silver(I)-N-Heterocyclic Carbene Complex Formation. Spectrochim. Acta. A Mol. Biomol. Spectrosc. 2020, 228, 117851. doi:10.1016/j.saa.2019.117851.

[99] Stefancu A, Aizpurua J, Alessandri I, Bald I, Baumberg JJ, Besteiro LV, et al. Impact of Surface Enhanced Raman Spectroscopy in Catalysis. ACS Nano 2024, 18, 29337-29379. doi:10.1021/acsnano.4c06192.

[100] Redolfi-Bristol D, Yamamoto K, Zhu W, Mazda O, Riello P, Marin E, et al. Mapping Selenium Nanoparticles Distribution Inside Cells through Confocal Raman Microspectroscopy. ACS Appl. Mater. Interfaces 2025, 17, 18124-18133. doi:10.1021/acsami.5c00380.

[101] Nakanishi W, Hayashi S, Katsura Y, Hada M. Relativistic Effect on ⁷⁷Se NMR Chemical Shifts of Various Selenium Species in the Framework of Zeroth-Order Regular Approximation. J. Phys. Chem. A 2011, 115, 8721-8730. doi:10.1021/jp202278f.

[102] Krivdin LB. Recent Advances in Computational Liquid-Phase ⁷⁷Se NMR. Russ. Chem. Rev. 2021, 90, 265-279. doi:10.1070/RCR4960.

[103] Hayashi S, Matsuiwa K, Nakanishi W. Relativistic Effect on ¹²⁵Te and ³³S NMR Chemical Shifts of Various Tellurium and Sulfur Species, Together with ⁷⁷Se of Selenium Congeners, in the Framework of Zeroth- Order Regular Approximation: Applicability to Tellurium Compounds. Rsc Adv. 2014, 4, 44795-44810. doi:10.1039/C4RA07818G.

[104] Paruzzo FM, Hofstetter A, Musil F, De S, Ceriotti M, Emsley L. Chemical Shifts in Molecular Solids by Machine Learning. Nat. Commun. 2018, 9, 4501. doi:10.1038/s41467-018-06972-x.

[105] Guan Y, Shree Sowndarya SV, Gallegos LC, St. John PC, Paton RS. Real-Time Prediction of ¹H and ¹³C Chemical Shifts with DFT Accuracy Using a 3D Graph Neural Network. Chem. Sci. 2021, 12, 12012-12026. doi:10.1039/D1SC03343C.

[106] Das A, Van Trieste GP, Powers DC. Crystallography of Reactive Intermediates. Comments Inorg. Chem. 2020, 40, 116-158. doi:10.1080/02603594.2020.1747054.

[107] Bui AH, Fernando Pulle AD, Micallef AS, Lessard JJ, Tuten BT. Dynamic Chalcogen Squares for Material and Topological Control over Macromolecules. Angew. Chem. Int. Ed. 2024, 63, e202404474. doi:10.1002/anie.202404474.

[108] Poddig H, Finzel K, Doert T. LaTe_1.82(1): Modulated Crystal Structure and Chemical Bonding of a Chalcogen-Deficient Rare Earth Metal Polytelluride. Acta Crystallogr. Sect. C Struct. Chem. 2020, 76, 530-540. doi:10.1107/S2053229620005094.

[109] Pandey S, Bean R, Sato T, Poudyal I, Bielecki J, Cruz Villarreal J, et al. Time-Resolved Serial Femtosecond Crystallography at the European XFEL. Nat. Methods 2020, 17, 73-78. doi:10.1038/s41592-019-0628-z.

[110] Marr ZY, Thapa Magar R, Fournier B, Benedict JB, Rack JJ. Photocrystallography of [Ru(bpy)₂(dmso)₂]²⁺ Reveals an O-Bonded Metastable State. Chem. Sci. 2023, 14, 7279-7284. doi:10.1039/D3SC01526B.

[111] Yannopoulos SN, Andrikopoulos KS. Raman Scattering Study on Structural and Dynamical Features of Noncrystalline Selenium. J. Chem. Phys. 2004, 121, 4747-4758. doi:10.1063/1.1780151.

[112] Georgiev D, Fernández-Galiana Á, Vilms Pedersen S, Papadopoulos G, Xie R, Stevens MM, et al. Hyperspectral Unmixing for Raman Spectroscopy via Physics-Constrained Autoencoders. Proc. Natl. Acad. Sci. USA 2024, 121, e2407439121. doi:10.1073/pnas.2407439121.

[113] McCamant DW, Kukura P, Mathies RA. Femtosecond Time-Resolved Stimulated Raman Spectroscopy: Application to the Ultrafast Internal Conversion in β-Carotene. J. Phys. Chem. A 2003, 107, 8208-8214. doi:10.1021/jp030147n.

[114] Chen C, Zhang W, Duan P, Liu W, Shafi M, Hu X, et al. SERS Enhancement Induced by the Se Vacancy Defects in Ultra-Thin Hybrid Phase SnSex Nanosheets. Opt. Express 2022, 30, 37795. doi:10.1364/OE.473965.

[115] Fei Z, Han Y, Gann E, Hodsden T, Chesman ASR, McNeill CR, et al. Alkylated Selenophene-Based Ladder-Type Monomers via a Facile Route for High-Performance Thin-Film Transistor Applications. J. Am. Chem. Soc. 2017, 139, 8552-8561. doi:10.1021/jacs.7b03099.

[116] Intemann JJ, Yao K, Yip H-L, Xu Y-X, Li Y-X, Liang P-W, et al. Molecular Weight Effect on the Absorption, Charge Carrier Mobility, and Photovoltaic Performance of an Indacenodiselenophene-Based Ladder-Type Polymer. Chem. Mater. 2013, 25, 3188-3195. doi:10.1021/cm401586t.

[117] Ashraf RS, Meager I, Nikolka M, Kirkus M, Planells M, Schroeder BC, et al. Chalcogenophene Comonomer Comparison in Small Band Gap Diketopyrrolopyrrole-Based Conjugated Polymers for High-Performing Field-Effect Transistors and Organic Solar Cells. J. Am. Chem. Soc. 2015, 137, 1314-1321. doi:10.1021/ja511984q.

[118] Liu X, Jiang X, Wang K, Miao C, Zhang S. Recent Advances in Selenophene-Based Materials for Organic Solar Cells. Materials 2022, 15, 7883. doi:10.3390/ma15227883.

[119] Wu Q, Wang W, Wu Y, Sun R, Guo J, Shi M, et al. Tailoring Polymer Acceptors by Electron Linkers for Achieving Efficient and Stable All-Polymer Solar Cells. Natl. Sci. Rev. 2022, 9, nwab151. doi:10.1093/nsr/nwab151.

[120] Liu Y, Yang Y, Chen C, Chen Q, Dou L, Hong Z, et al. Solution-Processed Small Molecules Using Different Electron Linkers for High-Performance Solar Cells. Adv. Mater. 2013, 25, 4657-4662. doi:10.1002/adma.201301716.

[121] Fan Q, Fu H, Wu Q, Wu Z, Lin F, Zhu Z, et al. Multi-Selenophene-Containing Narrow Bandgap Polymer Acceptors for All-Polymer Solar Cells with over 15% Efficiency and High Reproducibility. Angew. Chem. Int. Ed. 2021, 60, 15935-15943. doi:10.1002/anie.202101577.

[122] Lin F, Zuo L, Gao K, Zhang M, Jo SB, Liu F, et al. Regio-Specific Selenium Substitution in Non-Fullerene Acceptors for Efficient Organic Solar Cells. Chem. Mater. 2019, 31, 6770-6778. doi:10.1021/acs.chemmater.9b01242.

[123] Lin F, Jiang K, Kaminsky W, Zhu Z, Jen AKY. A Non-Fullerene Acceptor with Enhanced Intermolecular π-Core Interaction for High-Performance Organic Solar Cells. J. Am. Chem. Soc. 2020, 142, 15246-15251. doi:10.1021/jacs.0c07083.

[124] Radomska D, Czarnomysy R, Radomski D, Bielawski K. Selenium Compounds as Novel Potential Anticancer Agents. Int. J. Mol. Sci. 2021, 22, 1009. doi:10.3390/ijms22031009.

[125] Lu J, Vlamis-Gardikas A, Kandasamy K, Zhao R, Gustafsson TN, Engstrand L, et al. Inhibition of Bacterial Thioredoxin Reductase: An Antibiotic Mechanism Targeting Bacteria Lacking Glutathione. FASEB J. 2013, 27, 1394-1403. doi:10.1096/fj.12-223305.

[126] Ahmed F, Zhang D, Tang X, Malakar PK. Targeting Spore-Forming Bacteria: A Review on the Antimicrobial Potential of Selenium Nanoparticles. Foods 2024, 13, 4026. doi:10.3390/foods13244026.

[127] Barbosa NV, Nogueira CW, Nogara PA, De Bem AF, Aschner M, Rocha JBT. Organoselenium Compounds as Mimics of Selenoproteins and Thiol Modifier Agents. Metallomics 2017, 9, 1703-1734. doi:10.1039/C7MT00083A.

[128] Pan S, Yang J, Ji S, Li T, Gao S, Sun C, et al. Cancer Therapy by Targeting Thioredoxin Reductase Based on Selenium-Containing Dynamic Covalent Bond. CCS Chem. 2020, 2, 225-235. doi:10.31635/ccschem.020.202000124.

[129] Zhang L, Duan D, Liu Y, Ge C, Cui X, Sun J, et al. Highly Selective Off-On Fluorescent Probe for Imaging Thioredoxin Reductase in Living Cells. J. Am. Chem. Soc. 2014, 136, 226-233. doi:10.1021/ja408792k.

[130] Chen M, Cao W, Wang J, Cai F, Zhu L, Ma L, et al. Selenium Atom-Polarization Effect Determines TrxR-Specific Recognition of Metallodrugs. J. Am. Chem. Soc. 2022, 144, 20825-20833. doi:10.1021/jacs.2c08802.

[131] Nogueira CW, Barbosa NV, Rocha JBT. Toxicology and Pharmacology of Synthetic Organoselenium Compounds: An Update. Arch. Toxicol. 2021, 95, 1179-1226. doi:10.1007/s00204-021-03003-5.

[132] Luan L, Du L, Shi W, Li Y, Zhang Q. Photodynamic Inactivation of Bacteria and Biofilms with Benzoselenadiazole-Doped Metal-Organic Frameworks. Molecules 2022, 27, 8908. doi:10.3390/molecules27248908.

[133] Boualia B, Sandeli AE, Boulebd H, Karci H, Dundar M, Özdemir İ, et al. Exploring the Antimicrobial Potential of New Selenium-N-Heterocyclic Carbene Complexes and Their Benzimidazolium Salts: Synthesis, Characterization, Biological Evaluation, and Docking Insights. Chem. Pap. 2025, 79, 1439-1454. doi:10.1007/s11696-024-03866-9.

[134] Zhou W, Wang L, Li F, Zhang W, Huang W, Huo F, et al. Selenium-Containing Polymer@Metal-Organic Frameworks Nanocomposites as an Efficient Multiresponsive Drug Delivery System. Adv. Funct. Mater. 2017, 27, 1605465. doi:10.1002/adfm.201605465.

[135] Shen Y, Xu G, Li J, Lin X, Yang F, Yang H, et al. Functional Ionic Liquid Polymer Stabilizer for High-Performance Perovskite Photovoltaics. Angew. Chem. Int. Ed. 2023, 62, e202300690. doi:10.1002/anie.202300690.

[136] Guan B, Yan R, Li R, Zhang X. Selenium as a Pleiotropic Agent for Medical Discovery and Drug Delivery. Int. J. Nanomed. 2018, 13, 7473-7490. doi:10.2147/IJN.S181343.

[137] Gupta M, Gupta S. An Overview of Selenium Uptake, Metabolism, and Toxicity in Plants. Front. Plant Sci. 2017, 7, 1-14. doi:10.3389/fpls.2016.02074.

[138] Misra S, Hamilton C, Niyogi S. Induction of Oxidative Stress by Selenomethionine in Isolated Hepatocytes of Rainbow Trout (Oncorhynchus mykiss). Toxicol. In Vitro 2012, 26, 621-629. doi:10.1016/j.tiv.2012.02.001.

[139] Brown TA, Shrift A. Selenium: Toxicity and Tolerance in Higher Plants. Biol. Rev. 1982, 57, 59-84. doi:10.1111/j.1469-185X.1982.tb00364.x.

[140] Khurana A, Tekula S, Saifi MA, Venkatesh P, Godugu C. Therapeutic Applications of Selenium Nanoparticles. Biomed. Pharmacother. 2019, 111, 802-812. doi:10.1016/j.biopha.2018.12.146.

[141] Ferro C, Florindo HF, Santos HA. Selenium Nanoparticles for Biomedical Applications: From Development and Characterization to Therapeutics. Adv. Healthc. Mater. 2021, 10, 2100598. doi:10.1002/adhm.202100598.

[142] Zheng N, Wang Q, Li C, Wang X, Liu X, Wang X, et al. Responsive Degradable Theranostic Agents Enable Controlled Selenium Delivery to Enhance Photothermal Radiotherapy and Reduce Side Effects. Adv. Healthc. Mater. 2021, 10, 2002024. doi:10.1002/adhm.202002024.

[143] Roy P, Periasamy AP, Lin C-Y, Her G-M, Chiu W-J, Li C-L, et al. Photoluminescent Graphene Quantum Dots for In Vivo Imaging of Apoptotic Cells. Nanoscale 2015, 7, 2504-2510. doi:10.1039/C4NR07005D.

[144] Shi Z, Zhang H, Khan K, Cao R, Xu K, Zhang H. Two-Dimensional Selenium and Its Composites for Device Applications. Nano Res. 2022, 15, 104-122. doi:10.1007/s12274-021-3493-x.

[145] Moustafa H, Kangsabanik J, Bertoldo F, Manti S, Thygesen KS, Jacobsen KW, et al. Selenium and the Role of Defects for Photovoltaic Applications. Phys. Rev. Mater. 2024, 8, 015402. doi:10.1103/PhysRevMaterials.8.015402.

[146] Choudhary K, DeCost B, Chen C, Jain A, Tavazza F, Cohn R, et al. Recent Advances and Applications of Deep Learning Methods in Materials Science. NPJ Comput. Mater. 2022, 8, 59. doi:10.1038/s41524-022-00734-6.