Luminescent Heterotrinuclear Complexes with Pt(diimine)(dithiolate) and Metal Diphosphine as Components

Abstract

Reactions of Pt(diimine)(tdt) (tdt =3,4-toluenedithiolate) with [M(2)(dppm)(2)(MeCN)(2)](2+) (M = Cu(I) or Ag(I), dppm = bis(diphenylphosphino)methane) gave heterotrinuclear complexes [PtCu(2)(tdt)(mu-SH)(dppm)(3)](ClO(4)) (1) and [PtCu(2)(diimine)(2)(tdt)(dppm)(2)](ClO(4))(2) (diimine = 2,2'-bpyridine (bpy) 2; 4,4'-dimethyl-2,2'-bipyridine (dmbpy) 3; phenanthroline (phen) 4, 5-bromophenanthroline (Brphen) 5) for M = Cu(I), but [PtAg(2)(tdt)(mu-SH)(dppm)(3)](SbF(6)) (6) and [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (diimine = bpy 7; dmbpy 8; phen 9; Brphen 10) for M = Ag(I). While the complexes [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (7-10) result from linkage of Pt(diimine)(tdt) and [M(2)(dppm)(2)(MeCN)(2)](2+) by tdt sulfur donors, formation of [PtCu(2)(diimine)(2)(tdt)(dppm)(2)](ClO(4))(2) (2-5) is related to rupture of metal-ligand bonds in the metal components and recombination between the ligands and the metal atoms by self-assembly. The formation of 1 and 6 is involved not only in dissociation and recombination of the metal components, but also in disruption of C-S bonds in the dithiolate (tdt). The dithiolate tdt adopts a chelating and bridging coordination mode in anti conformation for [PtCu(2)(diimine)(2)(tdt)(dppm)(2)](ClO(4))(2) (2-5), whereas there is the syn conformation for other complexes. Compounds 1 and 6 represent sparse examples of mu-SH-bridged heterotrinuclear Pt(II)M(I)(2) complexes, in which Pt(II)-M(I) centers are bridged by dppm and sulfur donors of tdt, whereas M(I)-M(I) (M = Cu for 1; Ag for 6) centers are linked by dppm and the mu-SH donor. The (31)P NMR spectra show typical platinum satellites (J(Pt-P) = 1450-1570 Hz) for 1-6 and Ag-P coupling for Pt(II)-Ag(I) (J(Ag-P) = 350-450 Hz) complexes 6-10. All of the complexes show intense emission in the solid state and in frozen glasses at 77 K. The complexes [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (7-10) also afford emission in fluid acetonitrile solutions at room temperature. Solid-state emission lifetimes at room temperature are in the microsecond range. It is revealed that emission energies of the trinuclear heterometallic complexes [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (7-10) exhibit a remarkable blue shift (0.10-0.35 eV) relative to those of the precursor compounds Pt(diimine)(tdt). The crystal structures of 1, 2, 4, 6, 8, and 9 were determined by X-ray crystallography.

Luminescent PtII−MI (M = Cu, Ag, Au) Heteronuclear Alkynyl Complexes Prepared by Reaction of [Pt(C⋮CR)4]2- with [M2(dppm)2]2+ (dppm = Bis(diphenylphosphino)methane)

“…In the 31 P NMR spectra of Pt II −M I heteronuclear compounds 1 − 13 , typical P satellite peaks arising from the Pt−P coupling occur at 8.3−13.6 ppm with the J Pt - P value in the range of 1220−1300 Hz. 10a, In some cases, the Pt−P satellite signals show a moderate splitting that originates from the P−P couplings through P −CH 2 − P or/and P −Pt− P pathways with 2 J P - P = 30−35 Hz. For Pt II −Ag I heteronuclear compounds 1 − 5 and 13 , the P donors bound to the Ag I centers afford doublets or doublet of doublets centered at 1.6−2.7 ppm because of the effects of both Ag−P and P−P couplings with 1 J Ag - P = 515−530 Hz and 2 J P - P = 30−35 Hz.…”

“…Considerable attention has been paid to the chemistry of Pt II −M I (M = Cu, Ag, Au) heterometallic alkynyl complexes in recent years, primarily arising from their intriguing spectroscopic behavior, rich photophysical properties, and diversified structural topology. − One of the most intriguing features in these complexes is the tendency to form d 8 −d 10 metal−metal contacts that frequently induce intriguing spectroscopic and optoelectronic properties. It has been demonstrated that participation of the phosphine ligands usually favors formation of ligand-bridged or -unsupported Pt II −M I clusters through d 8 −d 10 metal−metal interactions. − …”

“…We have been interested in design of Pt II −M I heterometallic cluster complexes that display d 8 −d 10 metal−metal interactions and long-lived luminescence by incorporation of the Pt II thiolate or alkynyl components with the M I diphosphine complexes. , Reaction of Pt(diimine)(dithiolate) with [M 2 ( μ -dppm) 2 ] 2+ gave rise to the formation of a series of Pt II −M I heteronuclear cluster thiolate complexes with diverse structures and intriguing photoluminescence . To promote this research, we have attempted to investigate the reactions of [Pt(C⋮CR) 4 ] 2- with [M 2 ( μ -Ph 2 PXPPh 2 ) 2 ] 2+ (X = NH, CH 2 ) 10a.…”

Structural and Photophysical Study on Heterobimetallic Complexes with d8–d10 Interactions Supported by Carborane Ligands: Theoretical Analysis of the Emissive Behaviour

“…Different origins have been proposed for the luminescence observed for complexes 2 a and 2 b , in which diimine ligands complete the M(d 10 ) coordination sphere, depending on the compound type and M(d 10 ). Although the assignments of such emissions are not based on theoretical studies, the proposed origins of the luminescence include neither metal‐centred (MC) transitions nor metal–metal interactions 4a…”

Assembly of [Tp*WS3Cu2]-Supported Coordination Polymers from Linkers with a Unique μ-Pyridyl Bridging Mode and Their Enhanced Third-Order Nonlinear Optical Performances

“…In this work, we demonstrated that the rare cases of μ-N bridging observed in this series of [Tp*WS 3 Cu 2 ]-supported coordination polymers 2 – 6 is facilitated by the shape and symmetry of the butterfly-shaped cluster core as well as the coordination flexibility of Cu­(I) centers. This assertion is counter-supported by that pyridyls exhibit normal bonding in coordination polymers supported by other types of cluster units. − ,− The C 3 symmetrical Tp* ligands may also contribute to this behavior, reminiscent of the noninnocent nature of Tp and Tp* in the formation of cuboidal [MoS 4 Fe 3 Cl 3 ]-type clusters. It is noteworthy that through the use of monotopic (py), ditopic (bipy and bpea), and tritopic (tpt) ligands, the dimensionality of the resulting coordination polymers goes from 1D ( 2 , 3 ) through 2D ( 4 , 5 ) to 3D ( 6 ).…”