Designing Copper(I) Iodide Clusters with tunable D-π-A ligands for Photocatalytic Thiocyanation

Designing Copper(I) Iodide Clusters with tunable D-π-A ligands for Photocatalytic Thiocyanation | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 29 October 2025 V1 Latest version Share on Designing Copper(I) Iodide Clusters with tunable D-π-A ligands for Photocatalytic Thiocyanation Authors : Yuhe Yang , Shilin Liu , Yiqing Su , Hongjie Shen , Deguang Huang 0000-0002-9034-2842 [email protected] , and Jian Zhang 0000-0003-3373-9621 Authors Info & Affiliations https://doi.org/10.22541/au.176172678.89648970/v1 Published Inorganic Chemistry Version of record Peer review timeline 175 views 181 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Text：Five D-π-A ligands and six copper(I) iodide complexes [Cu I n I n (L m ) n ] (m = 1-5, n = 2, 4) are designed for the study of photocatalytic thiocyanation of the C(sp 2 )–H bonds in arenes and heteroarenes. The findings suggest that the four nuclear [Cu I 4 I 4 (L 4 ) 4 ] cluster is of better effect on photocatalysis with reference to its superior light-harvesting ability and multi-electron transfer capability owing to its unique tetranuclear configuration. Thus, a synthesis of aryl thiocyanates by photoredox thiocyanation of anilines, phenols, and heteroarenes with NH 4 SCN is reported. The reactions proceed smoothly in air atmosphere at room temperature. The scope of the method is demonstrated with 24 examples with the yield up to 85%. The mechanism is proposed to involve a single-electron transfer process mediated by the photoexcited copper(I) cluster, generating a thiocyanato radical (SCN·) and initiating the subsequent radical pathway. The successful gram-scale synthesis demonstrates the practical utility and potential of this strategy for constructing aryl thiocyanates. Cite this paper: Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.70XXX Designing Copper(I) Iodide Clusters with tunable D-π-A ligands for Photocatalytic Thiocyanation Yuhe Yang, a,b Shilin Liu, a,b Yiqing Su, b Hongjie Shen, b and Deguang Huang* , b Jian Zhang* , b a Fuzhou University, College of Chemistry and Materials Science, Fuzhou 350007, China b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China Ligand design| Metal behaviour | D-π-A ligands | Cu 4 I 4 cluster | photocatalysis | aryl C(sp²)–H activation | thiocyanation | para -regioselective Comprehensive Summary Text：Five D-π-A ligands and six copper(I) iodide complexes [Cu I n I n (L m ) n ] (m = 1-5, n = 2, 4) are designed for the study of photocatalytic thiocyanation of the C(sp²)–H bonds in arenes and heteroarenes. The findings suggest that the four nuclear [Cu I 4 I 4 (L 4 ) 4 ] cluster is of better effect on photocatalysis with reference to its superior light-harvesting ability and multi-electron transfer capability owing to its unique tetranuclear configuration. Thus, a synthesis of aryl thiocyanates by photoredox thiocyanation of anilines, phenols, and heteroarenes with NH 4 SCN is reported. The reactions proceed smoothly in air atmosphere at room temperature. The scope of the method is demonstrated with 24 examples with the yield up to 85%. The mechanism is proposed to involve a single-electron transfer process mediated by the photoexcited copper(I) cluster, generating a thiocyanato radical (SCN·) and initiating the subsequent radical pathway. The successful gram-scale synthesis demonstrates the practical utility and potential of this strategy for constructing aryl thiocyanates. Background and Originality Content Organic thiocyanates have attracted most attention for their diverse biological and pharmacological activities in natural products and drug molecules. [1] Among these, aryl thiocyanates serve as key precursors for constructing biologically active agrochemicals [2] and insecticides for seed storage, for example, 4-aminophenyl thiocyanates. Owing to their unique chemical structures and a wide range of biological activities, the incorporation of thiocyanate group into organic scaffolds caused great interests of scientists. To date, great progress was made in the thiocyanation of heterocyclic and aromatic compounds. A number of methodologies have been developed for the synthesis of aryl thiocyanates in the past decades (Scheme 1). Most of researches focused on nucleophilic substitution reactions induced by strong oxidants and/or acid such as HIO 4 , K 2 S 2 O 8 , graphene oxide, TBHP/NIS/AcOH (TBHP = tert-butyl hydroperoxide; NIS = N-iodosuccinimide) and trichloroisocyanuric acid. [3] In 2018 and Scheme 1 Synthetic strategies for thiocyanation reactions. soon afterwards, Chen and co-workers reported a new thiocyanation method using N-thiocyanato saccharin (NTSc) and N-thiocyano-dibenzenesulfonimide (NTSI) as the electrophilic reagents. [4] Cu-catalyzed cross-coupling [5] and electrocatalysis [6] were also employed to synthesize thiocyanates in the presence of acetic acid. More recently, Jain’s group and Rashid’s group developed photoredox-oxidation strategies for the regioselective C(sp²)-H thiocyanation of aromatic compounds, using eosin Y [7] and MgONPs@VCA (MgO nanoparticles coordinated with a vitamin C adduct) [8] as photocatalysts, respectively. Molecular oxygen was applied as a terminal oxidant in either situation. Despite these achievements, many challenges remain, including an excessive reliance on strong oxidants and/or corrosive systems, the use of stoichiometric metal salts, and the generation of toxic byproducts. Economy and high-performance of the catalytic system operation depend on photocatalysis, [9] readily available catalysts [10] and mild reaction conditions, [11] which are always objectives pursued by scientists. To our best knowledge, the development of photoactive Cu(I) catalysts for aromatic thiocyanation has not been reported. This motivates our research to study the design of a novel copper-based photocatalytic system for the direct thiocyanation of aromatic and heteroaromatic rings under simple conditions. [12] Photosensitizers are central to photocatalytic systems. The more advantages of metal-cluster photosensitizers had been demonstrated with their rational ligand design to optimize photophysical properties. [13] Multinuclear copper(I) iodide clusters featuring tunable D-π-A ligands exhibited enhanced visible light absorption and exceptional stability. Herein, we report the first [Cu I 4 I 4 (L) 4 ] (L = D-π-A ligands) photocatalytic protocol for direct regioselective C(sp²)-H thiocyanation of arenes and heteroarenes under UV-visible light irradiation, achieving efficient transformation with a broad substrate scope. Results and Discussion For a purpose of improving the photoconductive properties of copper(I) photocatalysts, [14] a couple of D-π-A ligands ( L 1 - L 5 ) were synthesized for the preparation of [Cu I n I n (L m ) n ] (m = 1-5, n = 2, 4) complexes. The ligands were designed in term of the coordination capability, conjugate effect, and electron donating ability (Figure 1). First, we started to study the effects of the donating groups on the absorption wavelength and efficiency of complexes. Stirring of L 1 and L 2 with CuI in the presence of PPh 3 as ancillary ligand afforded dimer Cu(I) complexes [Cu 2 I 2 (L 1 ) 2 (PPh 3 ) 2 ] ( PC1 ) and [Cu 2 I 2 (L 2 ) 2 (PPh 3 ) 2 ] ( PC2 ) in yields of 66% and 59%, respectively (Figure S2, Supporting Information). UV-Vis spectra showed that the biggest ultraviolet absorption peak of PC1 and PC2 were located between 315-320 nm with their absorption coefficient being from 21000-48000 L·mol -1 ·cm -1 . As a comparison, complexes [Cu 2 I 2 (L 3 ) 2 (PPh 3 ) 2 ] ( PC3 ) and [Cu 2 I 2 (L 4 ) 2 (PPh 3 ) 2 ] ( PC4 ) were prepared (Figure 2). Unexpectedly, with the replacement of the phenyl bridge by thiophene, the absorption wavelength and absorption efficiency of PC4 were improved greatly, although it did not have much effect on PC3 . Second, we focused on improving the proportion and the aggregation of metal cluster using L 4 as the target ligand. Complex [Cu 4 I 4 (L 4 ) 4 ] ( PC5 ) was obtained with the Cu···Cu distances ranging from 2.611(1) to 2.881(1) Å, which meant an almost uniform [Cu 4 I 4 ] cluster rather than the stacking of two [Cu 2 I 2 ] units perpendicular to each other. The interaction mechanisms between copper and iodine in [Cu 4 I 4 ] could be much different from that of [Cu 2 I 2 ] with the absorption coefficient increasing dramatically from 90000 to 165000 L·mol -1 ·cm -1 . [15] Third, we planned to elongate the bridge of ligand and L 5 was made. The change from thiophen ( L 4 ) to 2,2’-bithiophen ( L 5 ) was expected to extend the π-conjugation of ligand, elevate the HOMO energy level, strengthen electron donation to the pyridine acceptor, and enhance the visible-light harvesting of complex. In fact, complex [Cu 4 I 4 (L 5 ) 4 ] ( PC6 ) presented a similar [Cu 4 I 4 ] configuration to PC5 with the Cu···Cu distances of 2.632(1)-2.799(1) Å. It showed a significant red shift with the absorption maximum locating at 393 nm, which reflected the importance of bithiophene π-extension in broadening the spectral response. However, despite of the above achievement, PC6 displayed markedly lower absorption intensity than PC5 at their peak bands, indicating less gain in light utilization efficiency. Figure 1 UV-Vis spectra of complexes PC1 to PC6 . Based on the structural and optical characteristics, PC4 – PC6 were selected as photocatalysts for direct aromatic thiocyanation under UV-visible light irradiation (λ = 365 nm for PC4 and PC5, 390 nm for PC6 ). We started the research work by choosing aniline as the model substrates and explored the reaction by screening of catalyst, catalyst loading, solvent, and reaction time to find out the most appropriate conditions (Table 1). It is validated with test that reaction of aniline ( 1a ) and NH 4 SCN ( 2 ) in a ratio of 1 : 2, using PC5 (2 mol%) as the catalyst in MeCN and air atmosphere, irradiated by 365 nm LEDs (30 W) for 24 h gave the optimum result, providing the product 4-thiocyanatoaniline ( 3a ) in 77% yield based on aniline (entry 1). The use of PC4 and PC6 ( 390 nm LEDs for PC6, 30 W) as the catalysts under the same conditions resulted in lower yields of 35% and 45%, respectively (entries 2 and 3). Other copper source such as CuI and CuBr afforded the product in much lower yields (10-15%, entries 4 and 5). The absence of catalyst would cause no product unexpectedly (entry 6). A lower amount of PC5 (1 mol%) led to the generation of 3a in lower yield (55%, entry 7), but the addition of a greater amount of PC5 (4 mol%) did not help to improve the reaction efficiency (entry 8). The effect of the solvent was found to be essential for the proceeding of the reaction. Larger polar solvent was unfavorable for production with the decline of yield to trace Figure 2 Crystal structures of complexes PC4 , PC5 and PC6 . in DMF (entry 9). Less polar solvents, such as THF and dioxane, were of no advantage to the reaction (entries 10 and 11). In addition, a period of 24 h would be enough for the completion of the reaction. A shorter time (12 h) afforded the product in a low yield (52%, entry 12). A longer time (36 h) did not bring about obvious advantages in the production of 3a (80%, entry 13). Table 1 Optimization of the formation of 4-thiocyanatoanilines. a 1 PC5 2 mol% MeCN 24 h 77% 2 PC4 2 mol% MeCN 24 h 35% 3 PC6 2 mol% MeCN 24 h 45% 4 CuI 2 mol% MeCN 24 h 15% 5 CuBr 2 mol% MeCN 24 h 10% 6 None N/A MeCN 24 h None 7 PC5 1 mol% MeCN 24 h 55% 8 PC5 4 mol% MeCN 24 h 78% 9 PC5 2 mol% DMF 24 h trace 10 PC5 2 mol% THF 24 h 40% 11 PC5 2 mol% Dioxane 24 h 11% 12 PC5 2 mol% MeCN 12 h 52% 13 PC5 2 mol% MeCN 36 h 80% a Reaction conditions: 1a (0.25 mmol), 2 (0.5 mmol), PC5 (0.005 mmol, 2 mol%), solvent (1 mL), 365 nm LEDs (30 W), air, room temperature; b Isolated yields; En = Entry. With the optimized process conditions, we set out to explore the scope of substrates for the production of compounds 3 (Scheme 2). The diversity and versatility of the method were demonstrated with 24 examples varying by the positions of the substituents on benzene and the types of heterocycles. The yields of the reactions were discussed in view of the electronic effect, steric effect, and orientation effect of the functional groups on the substrates. First, experimental results indicated that the electronic effect on the benzene ring would have a large effect on production. Substitution of the electron-donating groups at the ortho position of the amine group would afford the products in yields of 82−85% ( 3b - 3d ). Substitution of the electron-withdrawing group, such as –I, −Br, and –Cl, at the same position would lead to a decline in production (61-71%, 3e - 3g ). Reaction of the substrates endowed with the strong electron-withdrawing groups –CF 3 decreased the yield dramatically down to 39% ( 3h ). With the substituent –NO 2 , the reaction provided the target product in trace ( 3i ). Second, the steric effect of substituents was studied by applying different groups to the benzene ring at the ortho and meta positions of the amine group. Substitution of the groups at the meta position had certain unfavorable effect on the reaction ( 3j - 3p ), but the substitution at the ortho position had little impact on production ( 3q - 3s ). Compared with the steric effect, the electronic effect had much greater influence on the production of 3 . Third, not only –NH 2 but also –NHMe, –NMe 2 , –OH were able to serve as the positioning groups for the proceeding of the reaction ( 3a , 3t - 3v ). Moreover, heterocycles were also suitable for our reaction. Indole and its derivative, 5-bromoindole, underwent smooth C3 -thiocyanation in our system, affording products 3w and 3x in yields of 76% and 80%, respectively. In contrast, 2,2’-bithiophene only proceeded C2 -thiocyanation with the production of 3y in 22% yield. The structure of 3a was determined by X-ray crystallography (Figure S2, Supporting Information). Scheme 2 Scope of Anilines and Heterocycles for Compounds 3. a a Reaction conditions: 1 (0.25 mmol), 2 (0.5 mmol), PC5 (0.005 mmol, 2 mol%), MeCN (1 mL), 365 nm LEDs (30 W), air, room temperature, 24 h, isolated yield. The synthetic utility of our reaction was examined by performing the experiment on the gram scale. Reactions of aniline (11 mmol) with NH 4 SCN (22 mmol) under the standard conditions afforded products 3a in 73% yield (Section 2.4, Supporting Information). The yield was not significantly reduced, demonstrating the potential application in the field of synthetic chemistry. Scheme 3 Control experiments. With the progress in the formation of 3 , a couple of experiments were conducted intentionally (Scheme 3). Addition of 2,2,6,6-tetramethylpiperidinooxy (TEMPO) to the above reaction completely inhibited the formation of 3a . It indicated that free radical reaction would be involved in the reaction pathway. This result was checked by the addition of 2,6-di-tert-butyl-4-methylphenol (BHT) as inhibitor, from which a BHT-SCN adduct was detected by the technique of HR-MS (Figure S1, Supporting Information). [7,16] No product could be obtained when the reaction was carried out under N 2 atmosphere, which meant that dioxygen might play an oxidation role to the photocatalytic reaction. However, experimental result showed that pure dioxygen conditions had some effects on production, likely due to over-oxidation of Cu(I) catalyst to Cu(II) species. Based on the above results and previous works, [17,18] a plausible mechanism is depicted in Scheme 4. Under 365 nm irradiation, the tetranuclear [Cu I 4 ] 4+ cluster ( PC5) is excited to its single state [Cu I 4 ] 4+* . The excited state oxidizes SCN - via single-electron transfer to generate thiocyanate radical (SCN·) with the reduction of cluster to [Cu 3 I Cu 0 ] 3+ . The SCN· radical attacks the carbon atom on the para position of amine, and radical intermediate A is formed . Oxidation of A leads to the formation of cation B . The intermediate B undergoes deprotonation to provide 3a . In the other hand, [Cu 3 I Cu 0 ] 3+ is oxidized by O 2 back to the starting cluster [Cu I 4 ] 4+ . Scheme 4 Proposed mechanism. Conclusions In summary, we have developed a tetranuclear copper(I) photoredox catalyst for direct regioselective thiocyanation of arenes and heteroarenes under UV-visible light irradiation. The method exhibits good functional group tolerance and provides a robust strategy for synthesizing pharmacologically relevant thiocyanates at room temperature. In the light of this work, it is easy to predict the future application of polynuclear copper clusters in asymmetric variants via chiral cluster design with extension to C(sp³)–H functionalization. Experimental The data underlying this study are available in the published article and its online supplementary material. Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Detailed experimental procedures, full characterization of products, X-ray crystallographic data, HR-MS spectra of BHT-SCN, NMR spectra of ligands L 1 - L 5 and compounds 3 . CCDC 2409383, 2494317, 2494349, 2494352-2494354 and 2494356 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected] , or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. Acknowledgement This research was supported by the Natural Science Foundation of Fujian Province (grant no. 2025J01252). Conflict of interest The authors declare no conflict of interest. References 1. (a) Castanheiro, T.; Suffert, J., Donnard; M., Gulea, M. Recent advances in the chemistry of organic thiocyanates. Chem. Soc. Rev. 2016 , 45(3), 494-505. (b) Rezayati, S.; Ramazani, A. A review on electrophilic thiocyanation of aromatic and heteroaromatic compounds. Tetrahedron. 2020 , 76(36), 131382. (c) Divyavani, C.; Padmaja, P.; Ugale, V. G.; Reddy, P. N. A review on thiocyanation of Indoles. Curr. Org. Synth. 2021 , 18(3), 233-247. (d) Chen, Y.; Wang, S.; Jiang, Q.; Cheng, C.; Xiao, X.; Zhu, G. Palladium-catalyzed site-selective sp 3 C-H bond thiocyanation of 2-aminofurans. J. Org. Chem. 2018 , 83(2), 716-722. 2. (a) Jin G.; M, Zhao G. Synthesis and Biological Activities of N-Thiophosphoryl-N’-Aroyl Aminothioureas. Chinese Journal of Applied Chemistry. 1995 , 12, 101-101. (b) Gomktsyan T. A.; Shainova R. S.; Karapetyan, A. V. Synthesis of Potential Biologically Active Compounds Based on Aryloxy-and Arylaminopropanehydrazides. Russ. J. Gen. Chem. 2020 , 90(7), 1181-1187. (c) Israfilova Z.; Taslimi, P.; Gülcin İ.; Abdullayev, Y.; Farzaliyev, V.; Karaman, M. Some thiocyanate containing heterocyclic compounds: Synthesis, bioactivity and molecular docking study. Chem. Select. 2023 , 8(3), e202203653. (d) Ji Ali J.; Feng X.; Zhao, J.; Liu Y.; Khan, K.A. Allyl isothiocyanate-induced tritrophic responses: Suppressing Myzus persicae and enhancing biological control in Brassica. Crop Protection, 2025 , 195, 107265. 3. (a) Mahajan, U. S., Akamanchi, K. G. Facile method for thiocyanation of activated arenes using iodic acid in combination with ammonium thiocyanate. Synth. Commun . 2009 , 39(15) , 2674-2682. (b) Mete, T. B.; Khopade, T. M.; Bhat, R. G. Transition-metal-free regioselective thiocyanation of phenols, ani-lines and heterocycles. Tetrahedron Lett . 2017 , 58(5) , 415-418. (c) Khalili, D. Graphene oxide: a promising carbocatalyst for the regioselective thiocyanation of aromatic amines, phenols, anisols and enolizable ketones by hydrogen peroxide/KSCN in water. New J. Chem . 2016 , 40(3) , 2547-2553. (d) Muniraj, N.; Dhineshkumar, J.; Prabhu, K. R. N-Iodosuccinimide Catalyzed Oxidative Selenocyanation and Thiocyanation of Electron Rich Arenes. Chem. Select . 2016 , 1(5) , 1033-1038. (e) Akhlaghinia, B.; Pourali, A. R.; Rahmani, M. Efficient and novel method for thiocyanation of aromatic compounds using trichloroisocyanuric acid/ammonium thiocyanate/wet SiO 2 . Synth. Commun . 2012 , 42(8) , 1184-1191. 4. (a) Wu, D.; Qiu, J.; Karmaker, P. G.; Yin, H.; Chen, F. X. N-Thiocyanatosaccharin: A “sweet” electrophilic thiocyanation reagent and the synthetic applications. J. Org. Chem . 2018 , 83(3) , 1576-1583. (b) Qiu, J.; Wu, D.; Karmaker, P. G.; Yin, H.; Chen, F. X. Enantioselective organocatalyzed direct α-thiocyanation of cyclic β-ketoesters by N-thiocyanatophthalimide. Org. Lett . 2018 , 20(6) , 1600-1603. 5. Noikham, M.; Yotphan, S. Copper-Catalyzed Regioselective Direct C-H Thiolation and Thiocyanation of Uracils. Eur. J. Org. Chem . 2019 , 2019(16) , 2759-2766. 6. Zhang, Y.; Gao, H.; Guo, J.; Zhang, H.; Yao, X. Selective electrochemical para-thiocyanation of aromatic amines under metal-, oxidant- and exogenous-electrolyte-free conditions. Chem. Comm . 2021 , 57(97) , 13166-13169. 7. Chauhan, P.; Ritu, Preeti.; Kumar, S.; Jain, N. Metal-Free and Visible-Light-Promoted C-3 Thiocyanation of 2-Arylquinolin-4-ones. Eur. J. Org. Chem . 2019 , 2019(27) , 4334-4340. 8. Kader, D. A.; Rashid, S. O. Regioselective direct thiocyanation of anilines and phenols using novel hybrid nanocatalyst (MgONPs@ VCA) under visible light induced photoredox catalysis. Mol. Catal . 2023 , 547 , 113409. 9. Yuan, J.; Zhang, L.; Zhang, X. M. Photocatalytic aerobic thiocyanation/sulfonylation of alkynes by DA type COFs: Enhanced generation of superoxide and sulfur-based radicals via building units adjusted band structures. J. Catal . 2024 , 429 , 115258. 10. (a) Feng, C.; Peng, Y.; Ding, G.; Li, X.; Cui, C.; Yan, Y. Catalyst and additive-free regioselective oxidative C-H thio/selenocyanation of arenes and heteroarenes with elemental sulfur/selenium and TMSCN. Chem. Comm . 2018 , 54(95) , 13367-13370. (b) Pramanik, M.; Das, S.; Babaahmadi, R.; Pahar, S.; Wirth, T.; Richards, E.; Melen, R. L. B (C 6 F 5 ) 3 -catalyzed selective C-H chalcogenation of arenes and heteroarenes. Chem . 2024 , 10(9) , 2901-2915. 11. (a) Zhang, Y.; Gao, H.; Guo, J.; Zhang, H.; Yao, X. Selective electrochemical para -thiocyanation of aromatic amines under metal-, oxidant-and exogenous-electrolyte-free conditions. Chem. Comm . 2021 , 57(97) , 13166-13169. (b) Moiseeva, N. V.; Sokolov, A. E.; Andreev, I. A.; Ratmanova, N. K.; Trushkov, I. V.; Kokorekin, V. A. Electrooxidative Thiocyanation of Hydroxy- and Alkoxybenzenes. Eur. J. Org. Chem . 2024 , 27(47) , e202400937. (c) Swain, S.; Panda, N. Electrochemical C-H Thiocyanation/Halogenation of 4-Arylthioazol-2-ones. Mol. Catal . 2025 , 583 , 115210. 12. (a) Dong, J. P.; Xu, Y.; Zhang, X. G.; Zhang, H.; Yao, L.; Wang, R.; Zang, S. Q. Copper-sulfur-nitrogen cluster providing a local proton for efficient carbon dioxide photoreduction. Angew. Chem. Int. Ed . 2023 , 135(48) , e202313648. (b) Xu, C.; Jin, Y.; Fang, H.; Zheng, H.; Carozza, J. C.; Pan, Y.; Han, H. A High-nuclearity copper sulfide nanocluster [S-Cu 50 ] featuring a double-shell structure configuration with Cu (II)/Cu (I) valences. J. Am. Chem. Soc . 2023 , 145(47) , 25673-25685. 13. (a) Wan, X. K.; Wang, J. Q.; Nan, Z. A.; Wang, Q. M. Ligand effects in catalysis by atomically precise gold nanoclusters. Sci. Adv . 2017 , 3(10) , e1701823. (b) He, J.; Bai, Z. Q.; Yuan, P. F.; Wu, L. Z.; Liu, Q. Highly Efficient Iridium-Based Photosensitizers for Thia-Paternò-Büchi Reaction and Aza-Photocyclization. ACS Catal . 2020 , 11(1) , 446-455. (c) Rentschler, M.; Schmid, M. A.; Frey, W.; Tschierlei, S.; Karnahl, M. Multidentate phenanthroline ligands containing additional donor moieties and their resulting Cu (I) and Ru (II) photosensitizers: A comparative study. Inorg. Chem . 2020 , 59(20) , 14762-14771. (d) Matus, M. F.; Häkkinen, H. Understanding ligand-protected noble metal nanoclusters at work. Nat. Rev. Mater . 2023 , 8(6) , 372-389. (e) Zhang, J.; Wu, Y.; Li, Y.; Lin, F.; Xiang, S.; Fan, X.; Zhang, Z. Molecular tweezers in thiolate-protected Cu (I) clusters: A framework platform for investigating ligand effects in cluster catalysis. Chin. Chem. Lett . 2025 , 111003. 14. (a) Nan, M. I.; Lakatos, E.; Giurgi, G. I.; Szolga, L.; Po, R.; Terec, A.; Roncali, J. Mono-and di-substituted pyrene-based donor-π-acceptor systems with phenyl and thienyl π-conjugating bridges. D&P . 2020 , 181 , 108527. (b) Liu, Y.; Wang, Y.; Pinna, N. Atomically precise metal nanoclusters for photocatalytic water splitting. ACS Mater. Lett . 2024, 6(7) , 2995-3006. (c) Zhu, X. Z.; Chen, S. H.; Xu, J. B.; Huang, J. H.; Yan, J. F.; Yuan, Y. F. Unveiling the Twisted Aromatic Donor Effect on the Nonlinear Response of D-π-A Type Malononitrile-Derived Chromophores. Chem. Eur. J . 2024 , 30(53) , e202402023. (d) Li, S.; Gao, C.; Yu, H.; Wang, Y.; Wang, S.; Ding, W.; Yu, J. Vinylene-Linked Donor-π-Acceptor Metal-Covalent Organic Framework for Enhanced Photocatalytic CO 2 Reduction. Angew. Chem. Int. Ed . 2024, 63(48) , e202409925. 15. (a) Zhuang, S.; Liao, L.; Zhao, Y.; Yuan, J.; Yao, C.; Liu, X.; Wu, Z. Is the kernel-staples match a key-lock match? Chem. Sci. 2018 , 9(9) , 2437-2442. (b) Rafiq, Q.; Khan, M. T.; Hayat, S. S.; Azam, S.; Rahman, A. U.; Elansary, H. O.; Shan, M. Adsorption and solar light activity of noble metal adatoms (Au and Zn) on Fe (III) surface: a first-principles study. PCCP . 2024 , 26(24) , 17118-17131. 16. (a) Songsichan, T.; Katrun, P.; Khaikate, O.; Soorukram, D.; Pohmakotr, M.; Reutrakul, V.; Kuhakarn, C. Thiocyanation of pyrazoles using KSCN/K 2 S 2 O 8 combination. SynOpen , 2018 , 2(01) , 0006-0016. (b) Savateev, A.; Ghosh, I.; König, B.; Antonietti, M. Photoredox catalytic organic transformations using heterogeneous carbon nitrides. Angew. Chem. Int. Ed . 2018 , 57(49) , 15936-15947. (c) Zeng, F. L.; Zhu, H. L.; Chen, X. L.; Qu, L. B.; Yu, B. Visible light-induced recyclable g-C 3 N 4 catalyzed thiocyanation of C(sp 2 )-H bonds in sustainable solvents. Green Chem . 2021 , 23(10) , 3677-3682. (d) Pan, J.; Liu, C.; Wang, J.; Dai, Y.; Wang, S.; Guo, C. Visible-light enabled C4-thiocyanation of pyrazoles by graphite-phase carbon nitride (g-C 3 N 4 ). Tetrahedron Lett . 2021 , 77 , 153253. (e) Huang, C.; Xie, Z. Z.; Gao, J.; Xiang, M.; Xiang, H. Y.; Chen, K.; Yang, H. Photosensitized Imino-Thiocyanation of Alkenes. Org. Lett . 2025 , 27(8) , 1979-1983. 17. (a) Fan, W.; Yang, Q.; Xu, F.; Li, P. A visible-light-promoted aerobic metal-free C-3 thiocyanation of indoles. J. Org. Chem . 2014 , 79(21) , 10588-10592. (b) Ma, Y.; Ma, J.; Wang, P.; Niu, J.; Zhang, J.; Duan, C.; Xu, H. Allochroic cluster light-emitting diodes based on unique μ3-tetraphosphine Cu 3 X 3 crowns with tunable excited states. Sci. Adv . 2024 , 10(1) , eadk3983. (c) Dong, H.; Wang, X.; Shi, P.; Chen, N.; Zhang, Z.; Yan, J.; Yi, H. N-Heterocyclic Carbene-Ligated Mixed-Valent Linear Cu 3 Cluster for Enhanced Electrocatalytic Nitrite Reduction. J. Am. Chem. Soc . 2025 . 18. (a) Wang, L.; Priebbenow, D. L.; Dong, W.; Bolm, C. N-arylations of sulfoximines with 2-arylpyridines by copper-mediated dual N-H/C-H activation. Org. Lett . 2014 , 16(10) , 2661-2663. (b) Xi, H.; Deng, B.; Zong, Z.; Lu, S.; Li, Z. Hydroxysulfenylation of electron-deficient alkenes through an aerobic copper catalysis. Org. Lett . 2015 , 17(5) , 1180-1183. (c) Salman, M.; Zhu, Z. Q.; Huang, Z. Z. Dehydrogenative cross-coupling reaction between N-aryl α-amino acid esters and phenols or phenol derivative for synthesis of α-aryl α-amino acid esters. Org. Lett . 2016 , 18(7) , 1526-1529. (d) Ji, X.; Li, D.; Zhou, X.; Huang, H.; Deng, G. J. Copper-catalyzed aerobic oxygenative cross dehydrogenative coupling of methyl ketones with para-C-H of primary anilines. Green Chem . 2017 , 19(3) , 619-622. (e) Jiang, H.; Yu, W.; Tang, X.; Li, J.; Wu, W. Copper-catalyzed aerobic oxidative regioselective thiocyanation of aromatics and heteroaromatics. J. Org. Chem . 2017 , 82(18) , 9312-9320. Manuscript received: XXXX, 2024 Manuscript revised: XXXX, 2024 Manuscript accepted: XXXX, 2024 Version of record online: XXXX, 2024 Left to Right: Authors Names You will be invited to submit the most recent photos of all the authors upon acceptance of the manuscript Entry for the Table of Contents Designing Copper(I) Iodide Clusters with tunable D-π-A ligands for Photocatalytic Thiocyanation Yuhe Yang, Shilin Liu, Yiqing Su, Hongjie Shen, and Deguang Huang* Jian Zhang* Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.70XXX A cubane-like [Cu I 4 I 4 (L 4 ) 4 ] cluster was designed with tunable D-π-A ligands for photocatalytic thiocyanation of arenes and heteroarenes to form aryl thiocyanates. Information & Authors Information Version history V1 Version 1 29 October 2025 Peer review timeline Published Inorganic Chemistry Version of Record 29 Apr 2026 Published Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords aryl c(sp²)–h activation cu4i4 cluster d-π-a ligands photocatalysis thiocyanation Authors Affiliations Yuhe Yang Fuzhou University College of Chemistry View all articles by this author Shilin Liu Fuzhou University College of Chemistry View all articles by this author Yiqing Su Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter View all articles by this author Hongjie Shen Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter View all articles by this author Deguang Huang 0000-0002-9034-2842 [email protected] Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter View all articles by this author Jian Zhang 0000-0003-3373-9621 Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter View all articles by this author Metrics & Citations Metrics Article Usage 175 views 181 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Yuhe Yang, Shilin Liu, Yiqing Su, et al. Designing Copper(I) Iodide Clusters with tunable D-π-A ligands for Photocatalytic Thiocyanation. Authorea . 29 October 2025. DOI: https://doi.org/10.22541/au.176172678.89648970/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . Format Please select one from the list RIS (ProCite, Reference Manager) EndNote BibTex Medlars RefWorks Direct import Tips for downloading citations document.getElementById('citMgrHelpLink').addEventListener('click', function() { popupHelp(this.href); return false; }); $(".js__slcInclude").on("change", function(e){ if ($(this).val() == 'refworks') $('#direct').prop("checked", false); $('#direct').prop("disabled", ($(this).val() == 'refworks')); }); View Options View options PDF View PDF Figures Tables Media Share Share Share article link Copy Link Copied! Copying failed. Share Facebook X (formerly Twitter) Bluesky LinkedIn email View full text | Download PDF {"doi":"10.22541/au.176172678.89648970/v1","type":"Article"} Now Reading: Share Figures Tables Close figure viewer Back to article Figure title goes here Change zoom level Go to figure location within the article Download figure Toggle share panel Toggle share panel Share Toggle information panel Toggle information panel Go to previous graphic Go to next graphic Go to previous table Go to next table All figures All tables View all material View all material xrefBack.goTo xrefBack.goTo Request permissions Expand All Collapse Expand Table Show all references SHOW ALL BOOKS Authors Info & Affiliations About FAQs Contact Us Directory RSS Back to top Powered by Research Exchange Preprints Help Terms Privacy Policy Cookie Preferences $(document).ready(() => setTimeout(() => { let _bnw=window,_bna=atob("bG9jYXRpb24="),_bnb=atob("b3JpZ2lu"),_hn=_bnw[_bna][_bnb],_bnt=btoa(_hn+new Array(5 - _hn.length % 4).join(" ")); $.get("/resource/lodash?t="+_bnt); },4000)); (function(){function c(){var b=a.contentDocument||a.contentWindow.document;if(b){var d=b.createElement('script');d.innerHTML="window.__CF$cv$params={r:'9ffa8e794dfa0700',t:'MTc3OTQzOTY1MA=='};var a=document.createElement('script');a.src='/cdn-cgi/challenge-platform/scripts/jsd/main.js';document.getElementsByTagName('head')[0].appendChild(a);";b.getElementsByTagName('head')[0].appendChild(d)}}if(document.body){var a=document.createElement('iframe');a.height=1;a.width=1;a.style.position='absolute';a.style.top=0;a.style.left=0;a.style.border='none';a.style.visibility='hidden';document.body.appendChild(a);if('loading'!==document.readyState)c();else if(window.addEventListener)document.addEventListener('DOMContentLoaded',c);else{var e=document.onreadystatechange||function(){};document.onreadystatechange=function(b){e(b);'loading'!==document.readyState&&(document.onreadystatechange=e,c())}}}})();