The First Examples of Platinum(II)−Cadmium(II) Bonds:  The Role of Strong Field Ligands in Making Dative Pt→M Bonds

Yamaguchi, Tadashi; Yamazaki, Fumie; Ito, Tasuku

doi:10.1021/ja991053n

Cited by 66 publications

(66 citation statements)

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“…Metal-metal bonds can act as a link between different subassemblies, making them a valuable tool in molecular or crystal engineering, and giving rise to a variety of structures, from simple linear bimetallic compounds to infinite one-dimensional chains [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30]. Furthermore, some of these complexes show interesting photophysical and photochemical properties [1][2][3][4][5]7,8,11,17,27,[29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48], which in some cases have been exclusively attributed to the presence...…”

Section: Introductionmentioning

confidence: 99%

“…M bonds [5,[12][13][14][15][16][17]21,22,26,[28][29][30]46,[49][50][51][52][53][54][55][56][57] the acidic M center being Cu(I), Ag(I), Au(I), Cd(II), Hg(II), Tl(I), Sn(II) and Pb(II). In the course of our recent research, we have studied the use of strong ligand field cyclometalated C^N ligands, such as 7,8-benzoquinolinate (bzq), in the coordination sphere of the Pt precursor [13,14,27,47].…”

Section: Introductionmentioning

confidence: 99%

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Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Baya

Belío

Forniés

et al. 2015

Inorganica Chimica Acta

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Luminescent complexes a b s t r a c t Complexes [Pt(C 6 F 5 )(bzq)(CNR)] {R = t Bu (1), 2-naphthyl (2), 2,6-Me 2 Ph (3)} have been prepared by replacement of the labile acetone in [Pt(C 6 F 5 )(bzq)(Me 2 CO)] with the corresponding isocyanide ligand. The structures 1 and 3 (X-ray) confirms their square planar geometry, with the bzq ligand coplanar to the metal plane. The reactions of 1-3 toward AgClO 4 lead to the trinuclear complexes [{Pt(C 6 F 5 ) (bzq)(CNR)} 2 Ag]ClO 4 {R = t Bu (4), 2-naphthyl (5)} or the tetranuclear [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6). The structures of these three polynuclear complexes have been established by X-ray diffraction studies. Two pseudo-polymorphs of 4 (4a and 4b), only differing in the crystallization solvent, have been found. 4a/b and 5 are trinuclear Pt-Ag-Pt complexes with a ''sandwich'' disposition. In all three cases, two ''Pt(C 6 F 5 )(bzq)(CNR)'' fragments are linked by a silver atom through Pt ? Ag bonds of donor acceptor nature and the silver center establishes a short g 1 interaction with the C ipso of the bzq ligands. Furthermore, the study of the structure of 6 reveals two ''(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph)PtAg'' subunits, each containing a Pt ? Ag bond related by an inversion center and held together through g 2 interactions established by the silver atom of one unit and one of the aromatic rings of the bzq ligand of the other. The reaction of 1-3 with [Ag(OClO 3 )(PPh 3 )] produces [(C 6 F 5 )(bzq)(CNR)PtAg(PPh 3 )]ClO 4 {R = t Bu, (7), 2-naphthyl (8), 2,6-Me 2 Ph (9)}. These dinuclear clusters contain a Pt ? Ag bond and show dynamic processes in solution (NMR) which involve the rupture and formation of these interactions. The X-ray structure of 7 confirms the presence of a Pt-Ag bond and a g 1 interaction with the C ipso of the bzq ligand (2.514(6) Å). All the crystal structures determined show pÁ Á Áp interactions of the bzq which stack in a parallel fashion with interplanar distances of ca. 3.3-3.4 Å. In 5 and 6 the aromatic fragments of the isocyanide ligands also take part in these pÁ Á Áp interactions. Absorption and emission properties of all the complexes 1-9 have been studied and explained with the aid of TD-DFT theoretical calculations.Compounds 1-9 are not emissive in solution but they are in rigid matrix. In glassy 2-Me-THF or CH 2 Cl 2 at 77 K the Pt/Ag compounds 4-9 at any concentration (10 À3 M, 10 À4 M, 10 À5 M) show the same emission spectra as their corresponding starting complexes 1-3, in line with the rupture of the Pt-Ag bonds. In the solid state only the dinuclear compounds [Pt(C 6 F 5 )(bzq)(CN-t Bu)AgPPh 3 ]ClO 4 (7) and [Pt(C 6 F 5 )(bzq) (CN-2,6-Me 2 Ph)AgPPh 3 ]ClO 4 (9) together with the tetranuclear complex [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6) are emissive at room temperature showing bright greenish (7, 9) or yellowish (6) phosphorescence. In all three compounds a significant contribution of M 0 orbitals (AgPPh 3 /Ag) to the frontier orbitals (FO) has been observed, and their main emissions see...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Baya

Belío

Forniés

et al. 2015

Inorganica Chimica Acta

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“…In fact, such electrostatic attractions have been shown to be particularly strong with platinate(ii) anions, as illustrated by the numerous examples of Pt II !M dativebond complexes (M = acid cation) presently known. [38][39][40] Following the report of the first luminescent and, unexpectedly, discrete six-coordinate platinumÀthallium complex Tl 2 Pt(CN) 4 , [41] there has been a growing interest in the chemical and photophysical properties of heteropolynuclear Tl I complexes. [5,[42][43][44][45][46][47][48][49][50] Of particular note are a peculiar paramagnetic [Tl{PtR 4 } 2 ]…”

Section: Introductionmentioning

confidence: 99%

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η²(π⋅⋅⋅Tl)‐Bonding Interactions

Berenguer

Forniés

Gil

et al. 2006

Chemistry A European J

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A novel series of [PtTl(2)(C[triple chemical bond]CR)(4)](n) (n = 2, R = 4-CH(3)C(6)H(4) (Tol) 1, 1-naphthyl (Np) 2; n = infinity, R = 4-CF(3)C(6)H(4) (Tol(F)) 3) complexes has been synthesized by neutralization reactions between the previously reported [Pt(C[triple chemical bond]CR)(4)](2-) (R = Tol, Tol(F)) or novel (NBu(4))(2)[Pt(C[triple chemical bond]CNp)(4)] platinum precursors and Tl(I) (TlNO(3) or TlPF(6)). The crystal structures of [Pt(2)Tl(4)(C[triple chemical bond]CTol)(8)]4 acetone, 14 acetone, [Pt(2)Tl(4)(C[triple chemical bond]CNp)(8)]3 acetone1/3 H(2)O, 23 acetone 1/3 H(2)O and [[PtTl(2)(C[triple chemical bond]CTol(F))(4)](acetone)S](infinity) (S = acetone 3 a; dioxane 3 b) have been solved by X-ray diffraction studies. Interestingly, whereas in the tolyl (1) and naphthyl (2) derivatives, the thallium centers exhibit a bonding preference for the electron-rich alkyne entities to yield crystal lattices based on sandwich hexanuclear [Pt(2)Tl(4)(C[triple chemical bond]CR)(8)] clusters (with additional Tlacetone (1) or Tlnaphthyl (2) secondary interactions), in the C(6)H(4)CF(3) (Tol(F)) derivatives 3 a and 3 b the basic Pt(II) center forms two unsupported Pt-Tl bonds. As a consequence 3 a and 3 b form an extended columnar structure based on trimetallic slipped PtTl(2)(C[triple chemical bond]CTol(F))(4) units that are connected through secondary Tl(eta(2)-acetylenic) interactions. The luminescent properties of these complexes, which in solution (blue; CH(2)Cl(2) 1,2; acetone 3) are very different to those in solid state (orange), have been studied. Curiously, solid-state emission from 1 is dependent on the presence of acetone (green) and its crystallinity. On the other hand, while a powder sample of 3 is pale yellow and displays blue (457 nm) and orange (611 nm) emissions, the corresponding pellets (KBr, solid) of 3, or the fine powder obtained by grinding, are orange and only exhibit a very intense orange emission (590 nm).

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“…Using emission as a signalling reporter, luminescent metal complexes are of interest due to their long emission lifetimes, tunable emission energies in the visible region and large Stokes shifts between absorption and emission spectra. [3] In our design of luminescent sensors for metal ions, we were attracted to the following: (1) [4] (2) crown ethers are known to complex metal ions; [5] (3) neutral organoplatinum() complexes are known to form dative bonds with divalent metal ions; [6] and (4) square-planar cyclometalated [7] and aromatic [8,9] diiminoplatinum() complexes possess rich photoluminescent properties that are sensitive to the microenvironment. Herein we describe the synthesis of [Pt(4-ethynylbenzo-15-crown-5) 2 (tBu 2 bpy)] (1) (tBu 2 bpy ϭ 4,4Ј-di-tert-butyl-2,2Ј-bipyridine) and [Pt(4-ethynylbenzo-15-crown-5)( …”

Section: Introductionmentioning

confidence: 99%

A Diiminoplatinum(II) Complex of 4‐Ethynylbenzo‐15‐crown‐5 as a Luminescent Sensor for Divalent Metal Ions

Siu

Lai

et al. 2003

Eur J Inorg Chem

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The binding of a diiminoplatinum(II) complex of 4‐ethynylbenzo‐15‐crown‐5 to divalent metal ions such as Mg2+ or Zn2+ is accompanied by substantial enhancement of emission intensity (1035‐ and 870‐fold increase, respectively, with 40 equivalents of metal salt) at λmax ≈︁ 555 nm; H+, Cd2+ and alkali‐metal ions cause minor enhancement of the photoluminescence (⩽ 10‐fold) under similar conditions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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The First Examples of Platinum(II)−Cadmium(II) Bonds: The Role of Strong Field Ligands in Making Dative Pt→M Bonds

Cited by 66 publications

References 14 publications

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η²(π⋅⋅⋅Tl)‐Bonding Interactions

A Diiminoplatinum(II) Complex of 4‐Ethynylbenzo‐15‐crown‐5 as a Luminescent Sensor for Divalent Metal Ions

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The First Examples of Platinum(II)−Cadmium(II) Bonds: The Role of Strong Field Ligands in Making Dative Pt→M Bonds

Cited by 66 publications

References 14 publications

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η2(π⋅⋅⋅Tl)‐Bonding Interactions

A Diiminoplatinum(II) Complex of 4‐Ethynylbenzo‐15‐crown‐5 as a Luminescent Sensor for Divalent Metal Ions

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Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η²(π⋅⋅⋅Tl)‐Bonding Interactions