Citation: Huahong ZHANG, Yang ZHAO, Rui NING, Shuixing WU, Xiaopeng ZHANG. Coordination equilibrium between cyclometalated Pt(Ⅱ) complexs [Pt(κ³-N^C^N′)(CNXyl)]Cl and [Pt(κ²-N^C^N′)(CNXyl)Cl][J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(9): 1840-1850. doi: 10.11862/CJIC.20250136 shu

Coordination equilibrium between cyclometalated Pt(Ⅱ) complexs [Pt(κ³-N^C^N′)(CNXyl)]Cl and [Pt(κ²-N^C^N′)(CNXyl)Cl]

College of Chemistry and Chemical Engineering, Key Laboratory of Water Pollution Treatment & Resource Reuse of Hainan Province, The International Joint Research Center for Clean and Efficient Utilization of Hydrocarbon Resources in the South China Sea of Hainan Province, Hainan Normal University, Haikou 571158, China

Corresponding author: Shuixing WU, shxwu@aliyun.com Xiaopeng ZHANG, zxp_inorganic@126.com
Received Date: 20 April 2025
Revised Date: 17 June 2025

Figures(8)

Reaction of the non-substituted/substituted unsymmetric pinene-derived complex [Pt(N^C^N′)Cl] with the aryl isocyanide 2,6-dimethylphenyl isocyanide (CNXyl) afforded a mixture of two isomeric species: the ionic complex [Pt(κ³-N^C^N′)(CNXyl)]Cl ([A]Cl) and the molecular complex [Pt(κ²-N^C^N′)(CNXyl)Cl] (B). Isomer B was almost the dominating product. The structures of the isomer B derivatives bearing —CF₃ and —Cl substituents on the pyridine ring of the pinene moiety (5B and 7B, respectively) have been confirmed by single-crystal X-ray diffraction, revealing a slightly distorted square planar geometry with trans-N_N^C^N′, CNR configuration (The terminal N atom of the κ²-N^C^N′ ligand is trans to the isocyanide ligand CNXyl.). Isomer B is thermodynamically more stable, as confirmed by theoretical calculations.
- coordination equilibrium,
- cyclometalated Pt(Ⅱ) complex,
- isocyanide,
- pinene group
1. [1]
  YUEN M Y, ROY V A L, LU W, KUI S C F, TONG G S M, SO M H, CHUI S S Y, MUCCINI M, NING J Q, XU S J, CHE C M. Semiconducting and electroluminescent nanowires self-assembled from organoplatinum(Ⅱ) complexes[J]. Angew. Chem.‒Int. Edit., 2008, 47: 9895-9899 doi: 10.1002/anie.200802981
2. [2]
  WANG P, LEUNG C H, MA D L, SUN R W Y, YAN S C, CHEN Q S, CHE C M. Specific blocking of CREB/DNA binding by cyclometalated platinum(Ⅱ) complexes[J]. Angew. Chem.‒Int. Edit., 2011, 50: 2554-2558 doi: 10.1002/anie.201006887
3. [3]
  LIU J, SUN R W Y, LEUNG C H, LOK C N, CHE C M. Inhibition of TNF-α stimulated nuclear factor-kappa B (NF-κB) activation by cyclometalated platinum(Ⅱ) complexes[J]. Chem. Commun., 2012, 48: 230-232 doi: 10.1039/C1CC15317J
4. [4]
  XIAO X S, LU W, CHE C M. Phosphorescent nematic hydrogels and chromonic mesophases driven by intra- and intermolecular interactions of bridged dinuclear cyclometalated platinum(Ⅱ) complexes[J]. Chem. Sci., 2014, 5: 2482-2488 doi: 10.1039/c4sc00143e
5. [5]
  CHEN Y, CHE C M, LU W. Phosphorescent organoplatinum(Ⅱ) complexes with a lipophilic anion: Supramolecular soft nanomaterials through ionic self-assembly and metallophilicity[J]. Chem. Commun., 2015, 51: 5371-5374 doi: 10.1039/C4CC08569H
6. [6]
  KUWABARA J, YAMAGUCHI K, YAMAWAKI K, YASUDA T, NISHIMURA Y, KANBARA T. Modulation of the emission mode of a Pt(Ⅱ) complex via intermolecular interactions[J]. Inorg. Chem., 2017, 56: 8726-8729 doi: 10.1021/acs.inorgchem.7b00880
7. [7]
  LIU Y, FENG J G, ZHANG B, WU Y C, CHEN Y, JIANG L. Regular aligned 1D single-crystalline supramolecular arrays for photodetectors[J]. Small, 2018, 14: 1701861 doi: 10.1002/smll.201701861
8. [8]
  WAN Q Y, TO W P, CHANG X, CHE C M. Controlled synthesis of Pd^Ⅱ and Pt^Ⅱ supramolecular copolymer with sequential multiblock and amplified phosphorescence[J]. Chem, 2020, 6: 945-967 doi: 10.1016/j.chempr.2020.01.021
9. [9]
  LIU M Y, HAN Y F, ZHONG H, ZHANG X L, WANG F. Supramolecular chirogenesis induced by platinum(Ⅱ) tweezers with excellent environmental tolerance[J]. Angew. Chem.‒Int. Edit., 2021, 60: 3498-3503 doi: 10.1002/anie.202012901
10. [10]
  YANG F, LI H Y, LI H J, HE X. Manipulation of 1D and 2D self-assembly via geometry modulation of adamantane isocyanide Pt(Ⅱ) complexes[J]. Chem. Commun., 2024, 60: 8605-8608 doi: 10.1039/D4CC02400A
11. [11]
  LU W, CHEN Y, ROY V A L, CHUI S S Y, CHE C M. Supramolecular polymers and chromonic mesophases self-organized from phosphorescent cationic organoplatinum(Ⅱ) complexes in water[J]. Angew. Chem.‒Int. Edit., 2009, 48: 7621-7625 doi: 10.1002/anie.200903109
12. [12]
  ZHANG X P, CHANG V Y, LIU J, YANG X L, HUANG W, LI Y, LI C H, MULLER G, YOU X Z. Potential switchable circularly polarized luminescence from chiral cyclometalated platinum(Ⅱ) complexes[J]. Inorg. Chem., 2015, 54: 143-152 doi: 10.1021/ic5019136
13. [13]
  LAI S W, LAM H W, LU W, CHEUNG K K, CHE C M. Observation of low-energy metal-metal-to-ligand charge transfer absorption and emission: Electronic spectroscopy of cyclometalated platinum(Ⅱ) complexes with isocyanide ligands[J]. Organometallics, 2002, 21: 226-234 doi: 10.1021/om0106276
14. [14]
  ZHANG H H, JING J, WU S X, LUO Y P, SUN S S, ZHANG D S, SHI Z F, ZHANG X P. Tunable circularly polarized luminescence of sol-gels based on chiral cyclometalated platinum(Ⅱ) complexes[J]. Dyes Pigment., 2022, 201: 110228 doi: 10.1016/j.dyepig.2022.110228
15. [15]
  CHEN Y, LU W, CHE C M. Luminescent pincer-type cyclometalated platinum(Ⅱ) complexes with auxiliary isocyanide ligands: Phase-transfer preparation, solvatomorphism, and self‑aggregation[J]. Organometallics, 2013, 32: 350-353 doi: 10.1021/om300965b
16. [16]
  JING J, XU G, ZHANG H H, CHEN X H, ZHANG D S, HAN L Z, QI X W, SHI Z F, ZHANG X P. Enhanced circularly polarized luminescence in fluoro-substituted N^C^N-coordinating platinum(Ⅱ) complexes[J]. Inorg. Chim. Acta, 2022, 541: 121067 doi: 10.1016/j.ica.2022.121067
17. [17]
  KNOF U, ZELEWSKY A V. Predetermined chirality at metal centers[J]. Angew. Chem.‒Int. Edit., 1999, 38: 302-322 doi: 10.1002/(SICI)1521-3773(19990201)38:3<302::AID-ANIE302>3.0.CO;2-G
18. [18]
  MAMULA O, ZELEWSKY A V. Supramolecular coordination compounds with chiral pyridine and polypyridine ligands derived from terpenes[J]. Coord. Chem. Rev., 2003, 242: 87-95 doi: 10.1016/S0010-8545(03)00062-6
19. [19]
  ZHANG H H, XU G, LV X S, WU S X, JING J, ZHAO Y, LIU J, CHRN X H, ZHANG X P. Mechanochromism and circularly polarized luminescence of chiral cyclometalated platinum(Ⅱ) complexes with different configurations and aggregated forms[J]. Dyes Pigment., 2024, 221: 111833 doi: 10.1016/j.dyepig.2023.111833
20. [20]
  SHELDRICK G M. A short history of SHELX[J]. Acta Crystallogr. Sect. A, 2008, A64: 112-122
21. [21]
  PERDEW J P, BURKE K, ERBZERHOF M. Generalized gradient approximation made simple[J]. Phys. Rev. Lett., 1996, 77: 3865-3868 doi: 10.1103/PhysRevLett.77.3865
22. [22]
  ADAMO C, BARONE V. Toward reliable density functional methods without adjustable parameters: The PBE0 model[J]. J. Chem. Phys., 1999, 110: 6158-6170 doi: 10.1063/1.478522
23. [23]
  GRIMME S, EHRLICH S, GOERIGK L. Effect of the damping function in dispersion corrected density functional theory[J]. J. Comput. Chem., 2011, 32: 1456-1465 doi: 10.1002/jcc.21759
24. [24]
  WEIGEND F, AHLRICHS R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy[J]. Phys. Chem. Chem. Phys., 2005, 7: 3297-3305 doi: 10.1039/b508541a
25. [25]
  FUKUI K. The path of chemical reactions‒the IRC approach[J]. Accounts Chem. Res., 1981, 14: 363-368 doi: 10.1021/ar00072a001
26. [26]
  PAZDERSKI L, PAWLAK T, SITKOWSKI J, KOZERSKI L, SZLYK E. ¹H, ¹³C, ¹⁵N and ¹⁹⁵Pt NMR studies of Au(Ⅲ) and Pt(Ⅱ) chloride organometallics with 2-phenylpyridine[J]. Magn. Reson. Chem., 2009, 47: 932-941 doi: 10.1002/mrc.2491
27. [27]
  HARPER B W J, ALDRICH-WRIGHT J R. The synthesis, characterisation and cytotoxicity of bisintercalating (2,2′∶6′,2″-terpyridine)platinum(Ⅱ) complexes[J]. Dalton Trans., 2015, 44: 87-96 doi: 10.1039/C4DT02773F
28. [28]
  EVSTIGNEEV M P, LANTUSHENKO A O, YAKOVLEVA Y A, SULEYMANOVA A F, ELTSOV O S, KOZHEVNIKOV V N. Tuning the aggregation of N^N^C Pt(Ⅱ) complexes by varying the aliphatic side chain and auxiliary halide ligand: ¹H and ¹⁹⁵Pt NMR investigation[J]. Eur. J. Inorg. Chem., 2019: 4122-4128
29. [29]
  ESTERUELAS M A, MORENO-BLÁZQUEZ S, OLIVÁN M, OÑATE E. Competition between N,C,N-pincer and N,N-chelate ligands in platinum(Ⅱ)[J]. Inorg. Chem., 2023, 62: 10152-10170 doi: 10.1021/acs.inorgchem.3c00694
30. [30]
  CHEN J L, LIN C H, CHEN J H, CHI Y, CHIU Y C, CHOU P T, LAI C H, LEE G H, CARTY A J. Reactions of the (2-pyridyl) pyrrolide platinum(Ⅱ) complex driven by sterically encumbered chelation: A model for the reversible attack of alcohol at the coordinated carbon monoxide[J]. Inorg. Chem., 2008, 47: 5154-5161 doi: 10.1021/ic800117v
31. [31]
  NAKATA N, IKEDA T, ISHII A. Syntheses of selenolato-bridged dinuclear hydridoplatinum complexes [Pt₂H₂(μ-Se^tBu)₂(PPh₃)₂] and [Pt₂H(Se^tBu)(μ-Se^tBu)₂(PPh₃)₂]: Unusual thermal reaction of hydrido(1, 1-dimethylethaneselenolato) platinum complex cis-[PtH(Se^tBu)(PPh₃)₂][J]. Inorg. Chem., 2010, 49: 8112-8116 doi: 10.1021/ic1011742
32. [32]
  ONGOMA P O, JAGANYI D. Mechanistic elucidation of linker and ancillary ligand substitution reactions in Pt(Ⅱ) dinuclear complexes[J]. Dalton Trans., 2013, 42: 2724-2734 doi: 10.1039/C2DT31956J
33. [33]
  ZUCCA A, CORDESCHI D, STOCCORO S, CINELLU M A, MINGHRTTI G, CHELUCCI G, MANASSERO M. Platinum(Ⅱ)-cyclometalated "roll-over" complexes with a chiral pinene-derived 2, 2′-bipyridine[J]. Organometallics, 2011, 30: 3064-3074 doi: 10.1021/om200172h
34. [34]
  DÍEZ Á, FORNIÉS J, LARRAZ C, LALINDE E, LÓPEZ J A, MARTÍN A, MORENO M T, SICILIA V. Structural and luminescence studies on π…π and Pt…Pt interactions in mixed chloro-isocyanide cyclometalated platinum(Ⅱ) complexes[J]. Inorg. Chem., 2010, 49: 3239-3251 doi: 10.1021/ic902094c
35. [35]
  MARTÍNEZ-JUNQUERA M, LARA R, LALINDE E, MORENO M T. Isomerism, aggregation-induced emission and mechanochromism of isocyanide cycloplatinated(Ⅱ) complexes[J]. J. Mater. Chem. C, 2020, 8: 7221-7233 doi: 10.1039/D0TC01163K
36. [36]
  MARTÍNEZ-JUNQUERA M, LALINDE E, MORENO M T. Multistimuli-responsive properties of aggregated isocyanide cycloplatinated(Ⅱ) complexes[J]. Inorg. Chem., 2022, 61: 10898-10914 doi: 10.1021/acs.inorgchem.2c01400
37. [37]
  SOKOLOVA E V, KINZHALOV M A, SMIRNOV A S, CHERANYOVA A M, IANOV D M, KUKUSHKIN V Y, BOKACH N A. Polymorph-dependent phosphorescence of cyclometalated platinum(Ⅱ) complexes and its relation to non-covalent interactions[J]. ACS Omega, 2022, 7: 34454-34462 doi: 10.1021/acsomega.2c04110
38. [38]
  BUTSCHKE B, SCHWARZ H. "Rollover" cyclometalation—Early history, recent developments, mechanistic insights and application aspects[J]. Chem. Sci., 2012, 3: 308-326 doi: 10.1039/C1SC00651G
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Coordination equilibrium between cyclometalated Pt(Ⅱ) complexs [Pt(κ3-N^C^N′)(CNXyl)]Cl and [Pt(κ2-N^C^N′)(CNXyl)Cl]

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通讯作者: 陈斌, bchen63@163.com

Coordination equilibrium between cyclometalated Pt(Ⅱ) complexs [Pt(κ³-N^C^N′)(CNXyl)]Cl and [Pt(κ²-N^C^N′)(CNXyl)Cl]