Synthesis, Characterization, and Optical Properties of Pentafluorophenyl Complexes with a Pt−Cd Bond

Abstract

Novel bimetallic neutral [(C6F5)4PtCd(cyclen)] and [(C6F5)2(C⋮CPh)2PtCd(cyclen)] (1, 2) and cationic [(C6F5)2(bzq)PtCd(cyclen)](ClO4) (3) pentafluorophenylplatinum(II)−cadmium(II) derivatives have been prepared by treatment of the adequate anionic starting precursors [Pt(C6F5)2X2] n - (n = 2, X = C6F5, C⋮CPh; n = 1, X2 = bzq) with Cd(ClO4)2 and cyclen. X-ray diffraction studies on complexes 1, 2, and 3 show that they are stabilized by a short Pt→Cd donor acceptor bond and, additionally, in complex 2 the Cd center is also coordinated to the Cα of one of the two alkynyl groups. In contrast, treatment of the binuclear compound [NBu4]2[Pt2(μ-Cl)2(C6F5)4] with [Cd(cyclen)(MeOH)2](ClO4)2 afforded the tetranuclear derivative [Pt(C6F5)2Cl(μ-Cl)Cd(cyclen)]2 (4) (X-ray), in which Pt and Cd atoms are connected by a μ3-Cl bridging ligand, and the binuclear cadmium complex [Cd2(μ-Cl)2(cyclen)2](ClO4)2 (5) (X-ray), in which two “Cd(cyclen)” fragments are bridged by two chlorine atoms. The photoluminescent properties of complexes 1−3 have also been examined and compared with those of their corresponding anionic parent compounds [NBu4]2[Pt(C6F5)4], [PMePh3]2[Pt(C6F5)2(C⋮CPh)2], and [NBu4][Pt(C6F5)2(bzq)] (6).

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

“…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...…”

“…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].…”

“…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]. Thus, the use of [Pt(bzq)(C 6 F 5 )(L)] nÀ (L = C 6 F 5 , n = 1 [13,14,27]; L = Me 2 CO, PPh 3 , pyPh 2 , tht, MeCN, n = 0 [30]) allowed us to prepare bimetallic complexes Pt-M (M = Cd [14], Ag [13,27,30]), trimetallic ''sandwich'' complexes Pt-Ag-Pt [13,30], or metallic infinite chain systems Á Á ÁPt-Ag-Pt-Ag-PtÁ Á Á [27,47].…”

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

“…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 ]…”

A Luminescent Heteronuclear Cluster Featuring an Unusual Cu6 Boat‐Shaped Core Assembled by Two Dialkynyl‐Cycloplatinated Units

“…[28,29,52] Mixed dimethylpyrazolatealkynyl hexanuclear clusters Pt 2 M 4 (M = Cu, Ag, Au) were prepared through double deprotonation of the coordinated pyrazoles in [cis-Pt(CϵCPh) 2 (Hdmpz) 2 ] by the corresponding metal ions. [17] Following our interest in heteropolynuclear benzoquinolinate platinum(II)-metal complexes, [53][54][55] we report here the synthesis and the photoluminescence of a Pt 2 Cu 6 cluster [Pt 2 Cu 6 (bzq) 2 (CϵC-C 5 H 4 N-2) 6 I 2 ] (1), generated by treat- [ …”