Platinum(II)‐Mediated Double Coupling of 2, 3‐Diphenylmaleimidine with Nitrile Functionalities To Give Annulated Pentaazanonatetraenate (PANT) Systems. Issue 10 (23rd February 2016)

• Record Type: Journal Article
• Authors: Ivanov, Daniil M.; Gushchin, Pavel V.; Novikov, Alexander S.; Avdontceva, Margarita S.; Zolotarev, Andrey A.; Starova, Galina L.; Chen, Yi‐Ting; Liu, Shih‐Hung; Chou, Pi‐Tai; Kukushkin, Vadim Yu.
• Is Part Of: European journal of inorganic chemistry. Issue 10(2016)
• Page Start: 1480
• Page End: 1487
• Publication Date: 2016-02-23
• Subjects: Platinum -- Metal‐mediated reactions -- N ligands -- Luminescence; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501398
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Treatment of trans ‐[PtCl2 (NCR)2 ] [R = Et1, n Pr2, t Bu3, CH2 Ph4, Ph5, p ‐CF3 C6 H4 6, NMe2 7, NEt2 8, N(CH2 )5 9 ] with 2.5 equiv. of 2, 3‐diphenylmaleimidine in CH2 Cl2 at room temperature for 5 min [for R = p ‐CF3 C6 H4 6, NMe2 7, NEt2 8, N(CH2 )5 9 ] or 14 h (for R = Et1, n Pr2, t Bu3, CH2 Ph4, Ph5 ) furnishes (1, 3, 5, 7, 9‐pentaazanona‐1, 3, 6, 8‐tetraenato)platinum(II) [(PANT)Pt II ; PtCl{H N =C(R)N=C N [C(Ph)=C(Ph)]C=NC(R)= N H}] complexes10 –18 . These species are formed by platinum(II)‐mediated double coupling of 2, 3‐diphenylmaleimidine with both nitrile ligands. The formulation of the complexes was supported by satisfactory C, H, and N elemental analyses, which were in agreement with HRESI‐MS, IR, and 1 H and 13 C{ 1 H} NMR spectra. The structures of10, 11· 1/8 n C6 H14, 15, 16· CCl4, and17· CHCl3 were determined by single‐crystal X‐ray diffraction. Absorption and emission studies were performed on representative complexes10, 15, and18, and the results show weak phosphorescence maxima at around 730–750 and 770–820 nm in CH2 Cl2 and in the solid state, respectively. Further insight into the photophysical properties was gained by time‐dependent density functional theory (TD–DFT) with detailed analysis of the corresponding frontier molecular orbitals for the lower‐lying transition. The calculated energies of the T1 state (in terms of wavelength) are 715.8 nm for10, 764.6 nm for15, and 697.7 nm for18, and these values are in good agreement with the trend of the first vibronic peaks of their phosphorescence spectra. Abstract : Nine (1, 3, 5, 7, 9‐pentaazanona‐1, 3, 6, 8‐tetraenate)platinum(II) [(PANT)Pt II ] complexes were synthesized by metal‐mediated organonitrile or dialkylcyanamide double coupling with 2, 3‐diphenylmaleimidine. The obtained PANT systems demonstrate phosphorescence both in solution and in the solid state.