Citation: Ruoxi RUN, Jikai ZHU, Lixia HAN, Zhiyin XIAO, Xiujuan JIANG, Jing JIN. Red light-induced CO-release from manganese carbonyl complexes[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(12): 2575-2583. doi: 10.11862/CJIC.20250132 shu

Red light-induced CO-release from manganese carbonyl complexes

Ruoxi RUN ¹ ,
Jikai ZHU ¹ ,
Lixia HAN ¹ ,
Zhiyin XIAO ¹ ,
Xiujuan JIANG ^1,, ,
Jing JIN ^2,,

1.
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China
2.
Affiliated Hospital of Jiaxing University, Jiaxing, Zhejiang 314001, China

Corresponding author: Xiujuan JIANG, jiangxj@mail.zjxu.edu.cn Jing JIN, jinjing@zjxu.edu.cn
Received Date: 18 April 2025
Revised Date: 10 October 2025

Figures(9)

In this work, three manganese carbonyl complexes [Mn(CO)₃(quino(CH=N)phX)Br] [X=Cl (1), Br (2), I (3)] were synthesized by a one-pot method using quinoline-2-carbaldehyde, halogenated aniline, and manganese pentacarbonyl bromide as starting materials. The structures of these complexes were characterized by NMR spectroscopy, single-crystal X-ray diffraction, infrared spectroscopy, and UV-Vis spectroscopy. Furthermore, the decomposition of these complexes under low-energy LED red light (λ=622-770 nm) was investigated by infrared spectroscopy and ultraviolet spectroscopy. The results indicate that these complexes exhibit excellent stability under dark conditions, while rapidly decomposing with carbon monoxide release (CO) upon irradiation of LED red light. Kinetic analysis revealed that the CO-releasing processes follow a first-order kinetic model, with the electronic effects of halogen substituents (Cl/Br/I) exerting significant influence on reaction rates. That is, the stronger the electron donor ability of the complex, the faster the reaction rate. Furthermore, the energy of the light source also plays a crucial role in the decomposition reaction of these complexes. Under certain conditions, the higher the light energy, the faster the decomposition rate of the complexes. Myoglobin assays further confirmed the generation of CO gas from complex 3 under light irradiation. Biocompatibility studies demonstrated significant cytotoxic effects of these complexes against cancer cells (RT112, IC₅₀=2-13 μmol·L^-1).
- manganese carbonyl complex,
- co-releasing molecules,
- photo-induced,
- first-order kinetics,
- cytotoxicity
1. [1]
  MOTTERLINI R, CLARK J E, FORESTI R, SARATHCHANDRA P, MANN B E, GREEN C J. Carbon monoxide-releasing molecules‒Characterization of biochemical and vascular activities[J]. Circ. Res., 2002, 90(2): E17-E24
2. [2]
  MARKS G S, BRIEN J F, NAKATSU K, MCLAUGHLIN B E. Does carbon monoxide have a physiological function?[J]. Trends Pharmacol. Sci., 1991, 12: 185-188 doi: 10.1016/0165-6147(91)90544-3
3. [3]
  OTTERBEIN L E, ZUCKERBRAUN B S, HAGA M, LIU F, SONG R, USHEVA A, STACHULAK C, BODYAK N, SMITH R N, CSIZMADIA E, TYAGI S, AKAMATSU Y, FLAVELL R J, BILLIAR T R, TZENG E, BACH F H, CHOI A M, SOARES M P. Carbon monoxide suppresses arteriosclerotic lesions associated with chronic graft rejection and with balloon injury[J]. Nat. Med., 2003, 9(2): 183-190 doi: 10.1038/nm817
4. [4]
  NETO J S, NAKAO A, KIMIZUKA K, ROMANOSKY A J, STOLZ D B, UCHIYAMA T, NALESNIK M A, OTTERBEIN L E, MURASE N. Protection of transplant-induced renal ischemia-reperfusion injury with carbon monoxide[J]. Am. J. Physiol. ‒Renal Physiol., 2004, 287(5): F979-F989 doi: 10.1152/ajprenal.00158.2004
5. [5]
  MOTTERLINI R, OTTERBEIN L E. The therapeutic potential of carbon monoxide[J]. Nat. Rev. Drug Discov., 2010, 9(9): 728-743 doi: 10.1038/nrd3228
6. [6]
  WU M L, HO Y C, YET S F. A central role of heme oxygenase-1 in cardiovascular protection[J]. Antioxid. Redox Signal., 2011, 15(7): 1835-1846 doi: 10.1089/ars.2010.3726
7. [7]
  WU L Y, WANG R. Carbon monoxide: Endogenous production, physiological functions, and pharmacological applications[J]. Pharmacol. Rev., 2005, 57(4): 585-630
8. [8]
  SCHATZSCHNEIDER U. Novel lead structures and activation mechanisms for CO-releasing molecules (CORMs)[J]. Brit. J. Pharmacol., 2015, 172(6): 1638-1650 doi: 10.1111/bph.12688
9. [9]
  HALILOVIC A, PATIL K A, BELLNER L, MARRAZZO G, CASTELLANO K, CULLARO G, DUNN M W, SCHWARTZMAN M L. Knockdown of heme oxygenase-2 impairs corneal epithelial cell wound healing[J]. J. Cell. Physiol., 2011, 226(7): 1732-1740 doi: 10.1002/jcp.22502
10. [10]
  MANSOUR A M, KHALED R M, SHEHAB O R. A comprehensive survey of Mn(Ⅰ) carbonyls as CO-releasing molecules reported over the last two decades[J]. Dalton Trans., 2024, 53(48): 19022-19057 doi: 10.1039/D4DT02091J
11. [11]
  MANSOUR A M, KHALED R M, FERRARO G, SHEHAB O R, MERLINO A. Metal-based carbon monoxide releasing molecules with promising cytotoxic properties[J]. Dalton Trans., 2024, 53(23): 9612-9656 doi: 10.1039/D4DT00087K
12. [12]
  BAG G, MUSIB D, RAZA M K, CASTONGUAY A, ROY M. Recent advances on the photo-chemotherapeutic potential of manganese carbonyl complexes[J]. Polyhedron, 2024, 249: 116778 doi: 10.1016/j.poly.2023.116778
13. [13]
  KHAN H, FAIZAN M, NIAZI S U K, MUHAMMAD M N, ZHANG W. Water-soluble carbon monoxide-releasing molecules (CORMs)[J]. Top. Curr. Chem., 2023, 381(1): 3
14. [14]
  ADACH W, BŁASZCZYK M, OLAS B. Carbon monoxide and its donors‒Chemical and biological properties[J]. Chem. ‒Biol. Interact., 2020, 318: 108973 doi: 10.1016/j.cbi.2020.108973
15. [15]
  YAN H, DU J, ZHU S, NIE G, ZHANG H, GU Z, ZHAO Y. Emerging delivery strategies of carbon monoxide for therapeutic applications: From CO gas to CO releasing nanomaterials[J]. Small, 2019, 15(49): 1904382 doi: 10.1002/smll.201904382
16. [16]
  FORD P C. Metal complex strategies for photo-uncaging the small molecule bioregulators nitric oxide and carbon monoxide[J]. Coord. Chem. Rev., 2018, 376: 548-564
17. [17]
  LIU J, LI R S, HE M, XU Z, XU L Q, KANG Y, XUE P. Multifunctional SGQDs-CORM@HA nanosheets for bacterial eradication through cascade-activated "nanoknife" effect and photodynamic/CO gas therapy[J]. Biomaterials, 2021, 277: 121084
18. [18]
  MEDE R, LORETT-VELASQUEZ V P, KLEIN M, GOERLS H, SCHMITT M, GESSNER G, HEINEMANN S H, POPP J, WESTERHAUSEN M. Carbon monoxide release properties and molecular structures of phenylthiolatomanganese(Ⅰ) carbonyl complexes of the type (OC)₄Mn(μ-S-aryl)₂[J]. Dalton Trans., 2015, 44(7): 3020-3033
19. [19]
  NOMURA N, TANAKA S, HIROTSU M, NISHIOKA T, NAKAJIMA H. Red-light responsive photoCORM activated in aqueous acid solution[J]. J. Organomet. Chem., 2023, 984: 122578
20. [20]
  HEMMERSBACH L, ADAM R, PLEVNALI C, ZHANG X, YARD B, SCHMALZ H G. Synthesis of bifunctional lipoxin-derived enzyme-triggered CO-releasing molecules (LipET-CORMs)[J]. Eur. J. Org. Chem., 2023, 26(9): e202201424
21. [21]
  JIANG X J, LONG L, WANG H L, CHEN L M, LIU X M. Diiron hexacarbonyl complexes as potential CO-RMs: CO-releasing initiated by a substitution reaction with cysteamine and structural correlation to the bridging linkage[J]. Dalton Trans., 2014, 43(26): 9968-9975
22. [22]
  KUNZ P C, MEYER H, BARTHEL J, SOLLAZZO S, SCHMIDT A M, JANIAK C. Metal carbonyls supported on iron oxide nanoparticles to trigger the CO-gasotransmitter release by magnetic heating[J]. Chem. Commun., 2013, 49(43): 4896-4898
23. [23]
  KOTTELAT E, FABIO Z. Visible light-activated PhotoCORMs[J]. Inorganics, 2017, 5(2): 692-710
24. [24]
  PIERRI A E, MUIZZI D A, OSTROWSKI A D, FORD P C. Photo-controlled release of NO and CO with inorganic and organometallic complexes//LO K K W. Luminescent and photoactive transition metal complexes as biomolecular probes and cellular reagents. Structure and bonding: Vol. 165[M/OL]. Berlin, Heidelberg: Springer, 2015: 1-45 [2025-10-15]. https://doi.org/10.1007/430_2014_164
25. [25]
  KHALED R M, FRIEDRICH A, RAGHEB M A, ABDEL-GHANI N T, MANSOUR A M. Cytotoxicity of photoactivatable bromo tricarbonyl manganese(Ⅰ) compounds against human liver carcinoma cells[J]. Dalton Trans., 2020, 49(27): 9294-9305
26. [26]
  CATALANO A, SINICROPI M S, IACOPETTA D, CERAMELLA J, MARICONDA A, ROSANO C, SCALI E, SATURNINO C, LONGO P. A review on the advancements in the field of metal complexes with Schiff bases as antiproliferative agents[J]. Appl. Sci. ‒Basel, 2021, 11(13): 6027
27. [27]
  WANG X M, ZHANG J D, JIN J, LI Z Q, MA M H, WANG H Y, JIANG X J, LIU X M. Visible light-induced CO-release from manganese carbonyl complexes based on Schiff base ligand[J]. Chinese J. Inorg. Chem., 2023, 39(4): 680-688
1. [1]
  Shengwen XU , Longlong YANG , Houji CAO , Deshuang TU , Xing WEI , Changsheng LU , Hong YAN . Research progress on light-induced functionalization of polyhedral carborane clusters. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2187-2200. doi: 10.11862/CJIC.20250192
2. [2]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012
3. [3]
  Jing JIN , Zhuming GUO , Zhiyin XIAO , Xiujuan JIANG , Yi HE , Xiaoming LIU . Tuning the stability and cytotoxicity of fac-[Fe(CO)₃I₃]^- anion by its counter ions: From aminiums to inorganic cations. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 991-1004. doi: 10.11862/CJIC.20230458
4. [4]
  Jiageng Li , Putrama . 数值积分耦合非线性最小二乘法一步确定反应动力学参数. University Chemistry, 2025, 40(6): 364-370. doi: 10.12461/PKU.DXHX202407098
5. [5]
  Tao Cao , Fang Fang , Nianguang Li , Yinan Zhang , Qichen Zhan . Green Synthesis of p-Hydroxybenzonitrile Catalyzed by Spinach Extracts under Red-Light Irradiation: Research and Exploration of Innovative Experiments for Pharmacy Undergraduates. University Chemistry, 2024, 39(5): 63-69. doi: 10.3866/PKU.DXHX202309098
6. [6]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
7. [7]
  Yue Wu , Jun Li , Bo Zhang , Yan Yang , Haibo Li , Xian-Xi Zhang . Research on Kinetic and Thermodynamic Transformations of Organic-Inorganic Hybrid Materials for Fluorescent Anti-Counterfeiting Application information: Introducing a Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(6): 390-399. doi: 10.3866/PKU.DXHX202403028
8. [8]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
9. [9]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
10. [10]
  Xiao-Qi Xu , Yapei Wang . Practice of Cultivating Multi-Disciplinary Talents with Comprehensive Skills through Demand-Driven, Individualized Education, and Humanities and Science Integration. University Chemistry, 2024, 39(6): 90-97. doi: 10.3866/PKU.DXHX202311049
11. [11]
  Jie Li , Huida Qian , Deyang Pan , Wenjing Wang , Daliang Zhu , Zhongxue Fang . Efficient Synthesis of Anethaldehyde Induced by Visible Light. University Chemistry, 2024, 39(4): 343-350. doi: 10.3866/PKU.DXHX202310076
12. [12]
  Tianlong Zhang , Jiajun Zhou , Hongsheng Tang , Xiaohui Ning , Yan Li , Hua Li . Virtual Simulation Experiment for Laser-Induced Breakdown Spectroscopy (LIBS) Analysis. University Chemistry, 2024, 39(6): 295-302. doi: 10.3866/PKU.DXHX202312049
13. [13]
  Junjian Wang , Qingquan Yu , Shunyao Liu , Yuke Chen , Xiaoyu Liu , Guodong Li , Xiaoyan Liu , Hong Liu , Weijia Zhou . Laser-Induced Carbonization of Hydroxyapatite Sandwich Paper for Inkless Printing. Acta Physico-Chimica Sinica, 2024, 40(4): 2304024-0. doi: 10.3866/PKU.WHXB202304024
14. [14]
  Jichao XU , Ming HU , Xichang CHEN , Chunhui WANG , Leichen WANG , Lingyi ZHOU , Xing HE , Xiamin CHENG , Su JING . Construction and hydrogen peroxide-activated chemodynamic activity of ferrocene?benzoselenadiazole conjugate. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1495-1504. doi: 10.11862/CJIC.20250144
15. [15]
  Linlin Wu , Yonghua Zhou , Zhongbei Li , Liu Deng , Younian Liu , Limiao Chen , Jianhan Huang . Digital Education Promoting Applied Chemistry Comprehensive Experiments: A Case Study of Catalytic Oxidation of Hydrogen Chloride and Reaction Kinetics. University Chemistry, 2025, 40(9): 273-278. doi: 10.12461/PKU.DXHX202411018
16. [16]
  Xinyu Xu , Jiale Lu , Bo Su , Jiayi Chen , Xiong Chen , Sibo Wang . Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂. Acta Physico-Chimica Sinica, 2025, 41(11): 100153-0. doi: 10.1016/j.actphy.2025.100153
17. [17]
  Jie WEI , Qing ZHOU , Dandan DING , Xiang JING , Fei LI . Photothermal toxicity of Prussian blue nanoparticles to cervical cancer cells. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2345-2357. doi: 10.11862/CJIC.20240435
18. [18]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . Efficient Photocatalytic Production of H₂O₂ over ZnO/D-A Conjugated Polymer S-scheme Heterojunction and Charge Transfer Dynamics Investigation. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-0. doi: 10.3866/PKU.WHXB202406027
19. [19]
  Hui-Ying Chen , Hao-Lin Zhu , Pei-Qin Liao , Xiao-Ming Chen . Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2306046-0. doi: 10.3866/PKU.WHXB202306046
20. [20]
  Jiahao Zeng , Hui Chao . 诱导程序性细胞死亡的金属抗肿瘤药物研究. University Chemistry, 2025, 40(6): 145-159. doi: 10.12461/PKU.DXHX202406019

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(81)
HTML views(13)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142