Citation: ZHU Chang-Li, WANG Wen-Yong, TIAN Dong-Mei, WANG Jiao, QIU Yong-Qing. Second-Order Nonlinear Optical Properties of Bis-Cyclometalated Iridium(Ⅲ) Isocyanide Complexes[J]. Acta Physico-Chimica Sinica, ;2015, 31(2): 245-252. doi: 10.3866/PKU.WHXB201412181 shu

Second-Order Nonlinear Optical Properties of Bis-Cyclometalated Iridium(Ⅲ) Isocyanide Complexes

1.
Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China

Received Date: 20 October 2014
Available Online: 18 December 2014
Fund Project: 国家自然科学基金(21173035)资助项目 (21173035)

The second-order nonlinear optical (NLO) properties of bis-cyclometalated iridium(Ⅲ) isocyanide complexes were investigated by density functional theory (DFT). In this work, the geometries of the complexes were optimized using the B3PW91(UB3PW91) functional and they were found to be in od agreement with experimental data. The 6-31G^* basis set was used for the non-metal elements while the LANL2DZ basis set was used for iridium. From the optimized geometries the total first hyperpolarizabilities (β_tot) of the complexes were calculated by the B3PW91(UB3PW91) and B3LYP(UB3LYP) functionals. Because the polarization and diffuse function may have a nontrivial effect on the calculation of the first hyperpolarizabiliy the more flexible and polarized 6-31+G^* non-metal atom basis sets and the LANL2DZ basis set for iridium were used. The absorption spectra of all the complexes were calculated at the CAM-B3LYP(UCAM-B3LYP)/6-31+G^** (LANL2DZ iridium atom) level in acetonitrile to obtain a deeper insight into the second-order NLO properties of these complexes. The results indicate that the second-order NLO response is not strongly affected by different substituents, while the redox reaction plays an important role in improving the second-order NLO response and this comes from a change in the charge transfer pattern and an increase in the degree of charge transfer. The β_tot values of the one-electron oxidized/reduced species (1a²⁺/1a)(complexes cyclometalated with N-arylazolesand alkyl isocyanides, [(C^∧N)₂Ir(CNR)₂]⁺ (R=CH₃)) are 75 and 144 times larger than that of the eigenstate complex (1a⁺), respectively. Therefore, the redox reaction of the cationic bis-cyclometalated iridium isocyanide complexes can effectively tune the second-order NLO properties.
- Bis-cyclometalated iridium(Ⅲ) isocyanide complex,
- Second-order nonlinear optical property,
- Density functional theory,
- Redox reaction,
- Charge transfer
1. [1]
  
  (1) Nalwa, H. S. Appl. Organomet. Chem. 1991, 5, 349.
2. [2]
  (2) Zhao, X. X.; Ma, J. P.; Dong, Y. B.; Huang, R. Q.; Lai, T. S. Cryst. Growth Des. 2007, 7, 1058. doi: 10.1021/cg060583+
3. [3]
  (3) Scarpaci, A.; Monnereau, C.; Hergué, N.; Blart, E.; Le upy, S.; Odobel, F.; rfo, A.; Pérez Moreno, J.; Clays, K.; Asselberghs, I. Dalton Trans. 2009, No. 23, 4358.
4. [4]
  (4) Coe, B. J.; Harris, J. A.; Jones, L. A.; Brunschwig, B. S.; Song, K.; Clays, K.; Garín, J.; Orduna, J.; Coles, S. J.; Hursthouse, M. B. J. Am. Chem. Soc. 2005, 127, 4845. doi: 10.1021/ja0424124
5. [5]
  (5) Coe, B. J.; Houbrechts, S.; Asselberghs, I.; Persoons, A. Angew. Chem. Int. Edit. 1999, 38, 366.
6. [6]
  (6) Liu, C. G.; Guan,W.; Song, P.; Yan, L. K.; Su, Z. M. Inorg. Chem. 2009, 48, 6548. doi: 10.1021/ic9004906
7. [7]
  (7) Liu, C. G.; Qiu, Y. Q.; Sun, S. L.; Li, N.; Yang, G. C.; Su, Z. M. Chem. Phys. Lett. 2007, 443, 163. doi: 10.1016/j.cplett.2007.06.060
8. [8]
  (8) Margeat, O.; Lacroix, P. G.; Costes, J. P.; Donnadieu, B.; Lepetit, C.; Nakatani, K. Inorg. Chem. 2004, 43, 4743. doi: 10.1021/ic049801j
9. [9]
  (9) Di Bella, S. Chem. Soc. Rev. 2001, 30, 355. doi: 10.1039/b100820j
10. [10]
  (10) Sun, J.; Sun, X. X.; Sun, S. L.; Qiu, Y. Q.; Li, C. B. Acta Phys. -Chim. Sin. 2011, 27 (10), 2297. [孙建, 孙秀欣, 孙世玲, 仇永清, 李传碧. 物理化学学报, 2011, 27 (10), 2297.] doi: 10.3866/PKU.WHXB20110938
11. [11]
  (11) Wang,W. Y.; Ma, N. N.; Sun, S. L.; Qiu, Y. Q. Organometallics 2014, 33, 3341.
12. [12]
  (12) Boixel, J.; Guerchais, V.; Le Bozec, H.; Jacquenmin, D.; Amar, A.; Boucekkine, A.; Colombo, A.; Dra netti, C.; Marinotto, D.; Roberto, D.; Righetto, S.; De Angelis, R. J. Am. Chem. Soc. 2014, 136, 5367. doi: 10.1021/ja4131615
13. [13]
  (13) Di Bella, S.; Dra netti, C.; Pizzotti, M.; Roberto, D.; Tessore, F.; U , R. Top. Organomet. Chem. 2010, 28, 1.
14. [14]
  (14) Li, X. J.; Sun, S. L.; Ma, N. N.; Sun, X. X.; Yang, G. C.; Qiu, Y. Q. J. Mol. Graph. Model. 2012, 33, 19. doi: 10.1016/j.jmgm.2011.11.002
15. [15]
  (15) Ma, N. N.; Sun, S. L.; Liu, C. G.; Sun, X. X.; Qiu, Y. Q. J. Phys. Chem. A 2011, 115, 13564. doi: 10.1021/jp206003n
16. [16]
  (16) Wang, C. H.; Ma, N. N.; Sun, X. X.; Sun, S. L.; Qiu, Y. Q.; Liu, P. J. J. Phys. Chem. A 2012, 116, 10496.
17. [17]
  (17) Sun, X. X.; Liu, Y.; Zhao, H. B.; Sun, S. L.; Liu, C. G.; Qiu, Y. Q. Acta Phys. -Chim. Sin. 2011, 27 (2), 315. [孙秀欣, 刘艳, 赵海波, 孙世玲, 刘春光, 仇永清. 物理化学学报, 2011, 27 (2), 315.] doi: 10.3866/PKU.WHXB20110236
18. [18]
  (18) Zhang, M. Y.; Ma, N. N.; Sun, S. L.; Sun, X. X.; Qiu, Y. Q.; Chen, B. J. Organomet. Chem. 2012, 718, 1. doi: 10.1016/j.jorganchem.2012.08.001
19. [19]
  (19) Zaarour, M.; Singh, A.; Latouche, C.;Williams, J. A. G.; Ledoux Rak, I.; Zyss, J.; Boucekkine, A.; Le Bozec, H.; Guerchais, V.; Dra netti, C.; Colombo, A.; Roberto, D.; Valore, A. Inorg. Chem. 2013, 52, 7987. doi: 10.1021/ic400541e
20. [20]
  (20) Shavaleev, N. M.; Monti, F.; Scopelliti, R.; Baschieri, A.; Sambri, L.; Armaroli, N.; Grätzel, M.; Nazeeruddin, M. K. Organometallics 2013, 32, 460. doi: 10.1021/om300894m
21. [21]
  (21) Sim, F.; Chin, S.; Dupuis, M.; Rice, J. E. J. Phys. Chem. 1993, 97, 1158. doi: 10.1021/j100108a010
22. [22]
  (22) Kanis, D. R.; Ratner, M. A.; Marks, T. J. Chem. Rev. 1994, 94, 195. doi: 10.1021/cr00025a007
23. [23]
  (23) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09, Revision A.02; Gaussian Inc.:Wallingford, CT, 2009.
24. [24]
  (24) Oudar, J. L. J. Chem. Phys. 1977, 67, 446. doi: 10.1063/1.434888
25. [25]
  (25) Janjua, M. R. S. A.; Guan,W.; Yan, L. K; Su, Z. M.; Karim, A.; Akbar, J. Eur. J. Inorg. Chem. 2010, 2010, 3466. doi: 10.1002/ejic.v2010:22
26. [26]
  (26) Karton, A.; Iron, M. A.; Van der Boom, M. E.; Martin, J. M. L. J. Phys. Chem. A 2005, 109, 5454.
27. [27]
  (27) Lu, T.; Chen, F.W. Acta Chim. Sin. 2011, 69, 2393. [卢天, 陈飞武. 化学学报, 2011, 69, 2393.] doi: 10.1021/jp0443456
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
3. [3]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
4. [4]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
5. [5]
  Tong Zhou , Jun Li , Zitian Wen , Yitian Chen , Hailing Li , Zhonghong Gao , Wenyun Wang , Fang Liu , Qing Feng , Zhen Li , Jinyi Yang , Min Liu , Wei Qi . Experiment Improvement of “Redox Reaction and Electrode Potential” Based on the New Medical Concept. University Chemistry, 2024, 39(8): 276-281. doi: 10.3866/PKU.DXHX202401005
6. [6]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
7. [7]
  Haiying Wei , Daqing Yang , Mingtao Run , Guoyan Huo . Examination and Analysis on Rationality of Experimental Design: Based on Reaction of Potassium Permanganate with Potassium Bormide. University Chemistry, 2024, 39(10): 283-288. doi: 10.12461/PKU.DXHX202404068
8. [8]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
9. [9]
  Yifei Cheng , Jiahui Yang , Wei Shao , Wanqun Zhang , Wanqun Hu , Weiwei Li , Kaiping Yang . Learning Goes Beyond the Written Word: Practical Insights from the “Leaf Electroplating” Popular Science Experiment. University Chemistry, 2024, 39(9): 319-327. doi: 10.3866/PKU.DXHX202310033
10. [10]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
11. [11]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
12. [12]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
13. [13]
  Xiutao Xu , Chunfeng Shao , Jinfeng Zhang , Zhongliao Wang , Kai Dai . Rational Design of S-Scheme CeO₂/Bi₂MoO₆ Microsphere Heterojunction for Efficient Photocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309031-. doi: 10.3866/PKU.WHXB202309031
14. [14]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
15. [15]
  Fan JIA , Wenbao XU , Fangbin LIU , Haihua ZHANG , Hongbing FU . Synthesis and electroluminescence properties of Mn²⁺ doped quasi-two-dimensional perovskites (PEA)₂Pb_yMn_1-yBr₄. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1114-1122. doi: 10.11862/CJIC.20230473
16. [16]
  Jianyin He , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . ZnCoP/CdLa₂S₄肖特基异质结的构建促进光催化产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2404030-. doi: 10.3866/PKU.WHXB202404030
17. [17]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026
18. [18]
  Fang Niu , Rong Li , Qiaolan Zhang . Analysis of Gas-Solid Adsorption Behavior in Resistive Gas Sensing Process. University Chemistry, 2024, 39(8): 142-148. doi: 10.3866/PKU.DXHX202311102
19. [19]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
20. [20]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201

Get Citation

PDF

XML

Metrics

PDF Downloads(359)
Abstract views(628)
HTML views(5)

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